Method for preparation of lithographic printing plate and lithographic printing plate precursor

ABSTRACT

A method for preparing a lithographic printing plate comprising: exposing a lithographic printing plate precursor comprising a hydrophilic support, a photosensitive layer containing (A) a sensitizing dye having an absorption maximum in a wavelength range of from 350 to 450 nm represented by the formula (I) or (II) as defined herein, (B) a polymerization initiator, (C) a polymerizable compound and (D) a hydrophobic binder polymer having an acid value of 0.3 meq/g or less and a protective layer provided in this order with a laser beam of from 350 to 450 nm; and rubbing a surface of the exposed lithographic printing plate precursor with a rubbing member in a presence of a developer having pH of from 2 to 10 in an automatic processor equipped with the rubbing member to remove the protective layer and an unexposed area of the photosensitive layer.

FIELD OF THE INVENTION

The present invention relates to a method for preparation of alithographic printing plate and a lithographic printing plate precursorfor use in the method.

BACKGROUND OF THE INVENTION

In general, a lithographic printing plate has a surface composed of anoleophilic image area and a hydrophilic non-image area. Lithographicprinting is a printing method comprising supplying alternately dampeningwater and oily ink on the surface of lithographic printing plate, makingthe hydrophilic non-image area a dampening water-receptive area (inkunreceptive area) and depositing the oily ink only to the oleophilicimage area by utilizing the nature of the dampening water and oily inkto repel with each other, and then transferring the ink to a printingmaterial, for example, paper.

In order to produce the lithographic printing plate, a lithographicprinting plate precursor (PS plate) comprising a hydrophilic supporthaving provided thereon an oleophilic photosensitive layer(image-recording layer) has heretofore been broadly used. Ordinarily, alithographic printing plate is obtained by conducting plate making by amethod of exposing the lithographic printing plate precursor through anoriginal, for example, a lith film, and then treating the exposedlithographic printing plate precursor to remove the photosensitive layerin the unnecessary non-image area by dissolving with a an alkalinedeveloper or an organic solvent thereby revealing a surface of thehydrophilic support to form the non-image area while leaving thephotosensitive layer in the image area.

In the hitherto known plate-making process of lithographic printingplate precursor, after the exposure, the step of removing theunnecessary photosensitive layer by dissolving, for example, with adeveloper is required. However, it is one of the subjects to simplifysuch an additional wet treatment described above. As one means for thesimplification, it has been desired to conduct the development with anearly neutral aqueous solution or simply with water.

On the other hand, digitalized technique of electronically processing,accumulating and outputting image information using a computer has beenpopularized in recent years, and various new image outputting systemsresponding to the digitalized technique have been put into practicaluse. Correspondingly, attention has been drawn to a computer-to-platetechnique of carrying the digitalized image information on highlyconverging radiation, for example, laser light and conducting scanningexposure of a lithographic printing plate precursor with the lightthereby directly preparing a lithographic printing plate without using alith film. Thus, it is one of the important technical subjects to obtaina lithographic printing plate precursor adaptable to the techniquedescribed above.

Based on the background described above, adaptation of plate makingoperation to both simplification and digitalization has been demandedstrongly more and more than ever before.

In response to such a demand, for instance, it is described in JP-A2002-365789 (the term “JP-A” as used herein means an “unexaminedpublished Japanese patent application”) that by incorporating a compoundhaving an ethylene oxide chain into an image-forming layer of alithographic printing plate precursor comprising a hydrophilic supportand the image-forming layer containing a hydrophobic precursor, ahydrophilic resin and a light to heat converting agent, the lithographicprinting plate precursor enables printing after conducting exposure andwet development processing using as a developer, water or an appropriateaqueous solution, besides on-machine development.

Also, a processing method of lithographic printing plate precursor isdescribed in U.S. Patent Publication No. 2004/0013968 which comprisespreparing a lithographic printing plate precursor comprising (i) ahydrophilic support and (ii) an oleophilic heat-sensitive layer whichcontains a radical-polymerizable ethylenically unsaturated monomer, aradical polymerization initiator and an infrared absorbing dye, ishardened with infrared laser exposure and is developable with an aqueousdeveloper containing 60% by weight or more of water and having pH of 2.0to 10.0, exposing imagewise the lithographic printing plate precursorwith an infrared laser, and removing the unhardened region of theheat-sensitive layer with the aqueous developer.

SUMMARY OF THE INVENTION

In order to maintain developing property to the aqueous developer havingpH of 2.0 to 10.0, however, it is necessary for the photosensitive layerto be hydrophilic or highly water-permeable, and it becomes a bigproblem to achieve a good balance between such hydrophilic or highlywater-permeable property of the photosensitive layer and thewater-resistance and film strength of the photosensitive layer afterexposure and hardening.

As a means to solve the problem, it is considered to increasesensitivity, specifically, to increase discrimination of the waterresistance between the unexposed area and the exposed area in a reactionsystem of high hardening efficiency. However, as well as the increase insensitivity, it is required not to form fog during handling under asafelight.

The present invention responds to the problem. Specifically, an objectof the invention is to provide a plate-making method in which alithographic printing plate precursor is developed with an aqueousdeveloper having pH of 2.0 to 10.0 to provide a good printing plate, anda lithographic printing plate precursor for use in the method which hashigh sensitivity and is excellent in safelight aptitude.

The inventor has found that the above-described object can be achievedby the following constructions.

-   (1) A method for preparation of a lithographic printing plate    comprising exposing a lithographic printing plate precursor    comprising a hydrophilic support, a photosensitive layer    containing (A) a sensitizing dye having an absorption maximum in a    wavelength range of 350 to 450 nm represented by formula (I) or (II)    shown below, (B) a polymerization initiator, (C) a polymerizable    compound and (D) a hydrophobic binder polymer having an acid value    of 0.3 meq/g or less and a protective layer provided in this order    with a laser beam of 350 to 450 nm, and rubbing a surface of the    exposed lithographic printing plate precursor with a rubbing member    in the presence of a developer having pH of 2 to 10 in an automatic    processor equipped with the rubbing member to remove the protective    layer and an unexposed area of the photosensitive layer:    wherein R¹ to R¹⁴ each independently represents a hydrogen atom, an    alkyl group, an alkoxy group, a cyano group or a halogen atom,    provided that at least one of R¹ to R¹⁰ represents an alkoxy group    having 2 or more carbon atoms; R¹⁵ to R³² each independently    represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano    group or a halogen atom, provided that at least one of R¹⁵ to R²⁴    represents an alkoxy group having 2 or more carbon atoms.-   (2) The method for preparation of a lithographic printing plate as    described in (1) above, wherein (B) the polymerization initiator is    a hexaarylbiimidazole compound.-   (3) The method for preparation of a lithographic printing plate as    described in (2) above, wherein the photosensitive layer further    contains (E) a chain transfer agent.-   (4) The method for preparation of a lithographic printing plate as    described in (3) above, wherein (E) the chain transfer agent is a    thiol compound represented by the following formula (T):    wherein R represents an alkyl group which may have a substituent or    an aryl group which may have a substituent; and A represents an    atomic group necessary for forming a 5-membered or 6-membered hetero    ring containing a carbon atom together with the N═C—N linkage, and A    may have a substituent.-   (5) The method for preparation of a lithographic printing plate as    described in any one of (1) to (4) above, wherein (D) the    hydrophobic binder polymer is at least one member selected from the    group consisting of a (meth)acrylic copolymer having a crosslinkable    group in a side chain or a polyurethane resin having a crosslinkable    group in a side chain.-   (6) The method for preparation of a lithographic printing plate as    described in any one of (1) to (5) above, wherein a part or all of    components of the photosensitive layer is encapsulated in a    microcapsule.-   (7) The method for preparation of a lithographic printing plate as    described in any one of (1) to (6) above, wherein the rubbing member    comprises at least two rotating brush rollers.-   (8) The method for preparation of a lithographic printing plate as    described in any one of (1) to (7) above, wherein the pH of the    developer is from 3 to 8.-   (9) The method for preparation of a lithographic printing plate as    described in any one of (1) to (8) above, wherein the exposed    lithographic printing plate precursor is subjected to a heat    treatment between the exposure and the development.-   (10) A lithographic printing plate precursor comprising a    hydrophilic support, a photosensitive layer containing (A) a    sensitizing dye having an absorption maximum in a wavelength range    of 350 to 450 nm represented by formula (I) or (II) shown below, (B)    a polymerization initiator, (C) a polymerizable compound and (D) a    hydrophobic binder polymer having an acid value of 0.3 meq/g or less    and a protective layer provided in this order, wherein the    protective layer and an unexposed area of the photosensitive layer    is capable of being removed by exposing the lithographic printing    plate precursor with a laser beam of 350 to 450 nm and rubbing a    surface of the exposed lithographic printing plate precursor with a    rubbing member in the presence of a developer having pH of 2 to 10    in an automatic processor equipped with the rubbing member:    wherein R¹ to R¹⁴ each independently represents a hydrogen atom, an    alkyl group, an alkoxy group, a cyano group or a halogen atom,    provided that at least one of R¹ to R¹⁰ represents an alkoxy group    having 2 or more carbon atoms; R¹⁵ to R³² each independently    represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano    group or a halogen atom, provided that at least one of R¹⁵ to R²⁴    represents an alkoxy group having 2 or more carbon atoms.-   (11) The lithographic printing plate precursor as described in (10)    above, wherein (B) the polymerization initiator is a    hexaarylbiimidazole compound.-   (12) The lithographic printing plate precursor as described in (11)    above, wherein the photosensitive layer further contains (E) a chain    transfer agent.-   (13) The lithographic printing plate precursor as described in (12)    above, wherein (E) the chain transfer agent is a thiol compound    represented by the following formula (T):    wherein R represents an alkyl group which may have a substituent or    an aryl group which may have a substituent; and A represents an    atomic group necessary for forming a 5-membered or 6-membered hetero    ring containing a carbon atom together with the N═C—N linkage, and A    may have a substituent.-   (14) The lithographic printing plate precursor as described in any    one of (10) to (13) above, wherein the exposed lithographic printing    plate precursor is subjected to a heat treatment between the    exposure and the development.-   (15) The method for preparation of a lithographic printing plate as    described in any one of (1) to (9) above, wherein the developer    contains a surfactant represented by the following formula (III) or    (IV):

In the formulae, R₁ to R₁₀ each represents a hydrogen atom or an alkylgroup; 1 represents an integer of 1 to 3; X₁ and X₂ each represents asulfonate, a sulfuric monoester salt, a carboxylate or a phosphate; andprovided that a total number of carbon atoms included in R₁ to R₅ or R₆to R₁₀ is 3 or more.

-   (16) The method for preparation of a lithographic printing plate as    described in any one of (1) to (9) above, wherein the developer    contains a surfactant represented by the following formula (V) or    (VI):

In the formulae, R₁ to R₁₀ each represents a hydrogen atom or an alkylgroup; 1 represents an integer of 1 to 3; X₁ and X₂ each represents asulfonate, a sulfuric monoester salt, a carboxylate or a phosphate; Y₁and Y₂ each represents —C_(n)H_(2n)—, —C_(n−m)H_(2(n−m))OC_(m)H_(2m)—,—O—(CH₂CH₂O)_(n)—, —O—(CH₂CH₂CH₂O)_(n)— or —CO—NH— wherein n≧1 andn≧m≧0; and provided that a total number of carbon atoms included in R₁to R₅ and Y₁ or R₆ to R₁₀ and Y₂ is 3 or more.

-   (17) The method for preparation of a lithographic printing plate as    described in any one of (1) to (9) above, wherein the developer    contains a surfactant represented by any on of the following    formulae (VII) to (IX):

In formula (VII), R_(a) represents a hydrogen atom or an alkyl group;and A and B each represents a group containing an ethylene oxide group,a carboxylic acid group or a carboxylate.

In formula (VIII), R_(b) and R_(c) each represents a hydrogen atom or analkyl group; C represents an alkyl group or a group containing anethylene oxide group; and D represents a group containing a carboxylicacid anion.

In formula (IX), R_(d), R_(e), R_(f) and R_(g) each represents ahydrogen atom or an alkyl group; and Z⁻ represents a counter anion.

According to the present invention, a plate-making method where alithographic printing plate precursor which has high sensitivity and isexcellent in safelight aptitude is developed with an aqueous developerhaving pH of 2.0 to 10.0 to prepare a good printing plate can beprovided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a structure of an automatic development processor.

Description of reference numerals and signs:

-   1: Rotating brush roller-   2: Backing roller-   3: Transport roller-   4: Transport guide plate-   5: Spray pipe-   6: Pipe line-   7: Filter-   8: Plate supply table-   9: Plate discharge table-   10: Developer tank-   11: Circulating pump-   12: Plate

DETAILED DESCRIPTION OF THE INVENTION

[Lithographic Printing Plate Precursor]

First, the lithographic printing plate precursor for use in theinvention is described in detail below.

<Photosensitive Layer>

The photosensitive layer of the lithographic printing plate precursoraccording to the invention contains (A) a sensitizing dye having anabsorption maximum in a wavelength range of 350 to 450 nm represented byformula (I) or (II) shown below, (B) a polymerization initiator, (C) apolymerizable compound and (D) a hydrophobic binder polymer having anacid value of 0.3 meq/g or less.

According to the above-described embodiment, a lithographic printingplate precursor which has high sensitivity at exposure with a laser beamof 350 to 450 nm and is excellent in safelight aptitude can be obtained.

The photosensitive layer may further contain other components, ifdesired. The constituting components of the photosensitive layer aredescribed in more detail below.

(A) Sensitizing Dye

The photosensitive layer according to the invention includes thesensitizing dye having an absorption maximum in a wavelength range of350 to 450 nm represented by the following formula (I) or (II):

wherein R¹ to R¹⁴ each independently represents a hydrogen atom, analkyl group, an alkoxy group, a cyano group or a halogen atom, providedthat at least one of R¹ to R¹⁰ represents an alkoxy group having 2 ormore carbon atoms; and R¹⁵ to R³² each independently represents ahydrogen atom, an alkyl group, an alkoxy group, a cyano group or ahalogen atom, provided that at least one of R¹⁵ to R²⁴ represents analkoxy group having 2 or more carbon atoms.

The alkyl group or alkoxy group may have a substituent and may be astraight-chain or branched form, but the branched form is preferable.Examples of the substituent include a halogen atom and a hydroxy group.

Also, the alkylene chain of the alkyl group or alkoxy group may includean ester bond, an ether bond or a thioether bond.

R¹, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ each independently preferablyrepresents a hydrogen atom, a fluorine atom or a chlorine atom. Inparticular, it is preferable that R¹, R⁵, R⁶ and R¹⁰ each represents ahydrogen atom, R² to R⁴ and R⁷ to R⁹ each independently represents analkoxy group, and at least two of R² to R⁴ and R⁷ to R⁹ each representsa branched alkoxy group having from 3 to 15 carbon atoms.

Also, it is especially preferable that R², R⁴, R⁷ and R⁹ each representsa methoxy group, and R³ and R⁸ each represents a branched alkoxy grouphaving from 3 to 15 carbon atoms.

R¹⁵, R¹⁹, R²⁰, R²⁴ and R²⁵ to R³² each independently preferablyrepresents a hydrogen atom, a fluorine atom or a chlorine atom. Inparticular, it is preferable that R¹⁵, R¹⁹, R²⁰ and R²⁴ each representsa hydrogen atom, R¹⁶ to R¹⁸ and R²¹ to R²³ each independently representsan alkoxy group, and at least two of R¹⁶ to R¹⁸ and R²¹ to R²³ eachrepresents a branched alkoxy group having from 3 to 15 carbon atoms.

Also, it is especially preferable that R¹⁶, R¹⁸, R²¹ and R²³ eachrepresents a methoxy group, and R¹⁷ and R²² each represents a branchedalkoxy group having from 3 to 15 carbon atoms.

Specific examples of the sensitizing dye having an absorption maximum ina wavelength range of 350 to 450 nm represented by formula (I) or (II)are set forth below, but the invention should not be construed as beinglimited thereto.

The sensitizing dye described above can be synthesized according toknown methods, for example, methods described in WO2005/029187.

Details of the method of using the sensitizing dye, for example,selection of the structure, individual or combination use or an amountadded, can be appropriately determined in accordance with thecharacteristic design of the final lithographic printing plateprecursor.

For instance, when two or more sensitizing dyes are used in combination,the compatibility thereof in a photosensitive composition constitutingthe photosensitive layer can be increased. For the selection ofsensitizing dye, the molar absorption coefficient thereof at theemission wavelength of the light source used is an important factor inaddition to the photosensitivity. Use of the dye having a large molarabsorption coefficient is profitable, because the amount of dye addedcan be made relatively small. Also, in case of using in a lithographicprinting plate precursor, the use of such a dye is advantageous in viewof physical properties of the photosensitive layer. Since thephotosensitivity and resolution of the photosensitive layer and thephysical properties of the exposed area of the photosensitive layer aregreatly influenced by the absorbance of sensitizing dye at thewavelength of light source, the amount of the sensitizing dye added isappropriately determined by taking account of these factors.

However, for the purpose of hardening a layer having a large thickness,for example, of 5 μm or more, low absorbance is sometimes rathereffective for increasing the hardening degree. In the case of using in alithographic printing plate precursor where the photosensitive layer hasa relatively small thickness, the amount of the sensitizing dye added ispreferably selected such that the photosensitive layer has an absorbancefrom 0.1 to 1.5, preferably from 0.25 to 1. Ordinarily, the amount ofthe sensitizing dye added is preferably from 0.05 to 30 parts by weight,more preferably from 0.1 to 20 parts by weight, and most preferably from0.2 to 10 parts by weight, per 100 parts by weight of the total solidcontent of the photosensitive layer.

(B) Polymerization Initiator

The polymerization initiator for use in the invention includes, forexample, a trihalomethyl compound, a carbonyl compound, an organicperoxide, an azo compound, an azide compound, a metallocene compound, ahexaarylbiimidazole compound, an organic boron compound, a disulfonecompound, an oxime ester compound and an onium salt compound. Amongthem, at least one compound selected from the group consisting of thehexaarylbiimidazole compound, onium salt compound, trihalomethylcompound and metallocene compound is preferable, and thehexaarylbiimidazole compound is particularly preferable. Thepolymerization initiators may be appropriately used in combination oftwo or more thereof.

The hexaarylbiimidazole polymerization initiator includes, for example,lophine dimers described in JP-B-45-37377 and JP-B-44-86516 (the term“JP-B” as used herein means an “examined Japanese patent publication”),specifically,

-   2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,-   2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetraphenylbiimidazole,-   2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,-   2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(m-methoxyphenyl)biimidazole,-   2,2′-bis(o,o′-dichlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole,-   2,2′-bis(o-nitrophenyl)-4,4′,5,5′-tetraphenylbiimidazole,-   2,2′-bis(o-methylphenyl)-4,4′,5,5′-tetraphenylbiimidazole and-   2,2′-bis(o-trifluoromethylphenyl)-4,4′,5,5′-tetraphenylbiimidazole.

The trihalomethyl compound preferably includestrihalomethyl-s-triazines, and specifically s-triazine derivativeshaving a tri-halogen-substituted methyl group described inJP-A-58-29803, for example, 2,4,6-tris(trichloromethyl)-s-triazine,2-methoxy-4,6-bis(trichloromethyl)-s-triazine,2-amino-4,6-bis(trichloromethyl)-s-triazine and2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine.

The onium salt includes, for example, onium salts represented by thefollowing formula (III):

In formula (III), R¹¹, R¹² and R¹³, which may be the same or different,each represents a hydrocarbon group having 20 or less carbon atoms whichmay have a substituent. Preferred examples of the substituent include ahalogen atom, a nitro group, an alkyl group having 12 or less carbonatoms, an alkoxy group having 12 or less carbon atoms and an aryloxygroup having 12 or less carbon atoms.

Z⁻ represents a counter ion selected from the group consisting of ahalogen ion, a perchlorate ion, a tetrafluoroborate ion, ahexafluorophosphate ion, a carboxylate ion and a sulfonate ion, and ispreferably a perchlorate ion, a hexafluorophosphate ion, a carboxylateion or an arylsulfonate ion.

The metallocene compound can be used by appropriately selecting, forexample, from known compounds described in JP-A-59-152396 andJP-A-61-151197. Specific examples thereof includedicyclopentadienyl-Ti-dichloride,

-   dicyclopentadienyl-Ti-bisphenyl,-   dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,-   dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,-   dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,-   dicyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,-   dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl,-   dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,-   dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,-   dimethylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl and-   bis(cyclopentadienyl)-bis-(2,6-difluoro-3-(pyr-1-yl)phenyl)titanium.

Examples of the carbonyl compound described above include, benzophenonederivatives, for example, benzophenone, Michler's ketone,2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone,2-chlorobenzophenone, 4-bromobenzophenone or 2-carboxybenzophenone,acetophenone derivatives, for example,2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone,1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropane,1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone,1-hydroxy-1-(p-dodecylphenyl)ketone,2-methyl-(4′-(methylthio)phenyl)-2-morpholino-1-propane or1,1,1,-trichloromethyl-(p-butylphenyl)ketone, thioxantone derivatives,for example, thioxantone, 2-ethylthioxantone, 2-isopropylthioxantone,2-chlorothioxantone, 2,4-dimetylthioxantone, 2,4-dietylthioxantone or2,4-diisopropylthioxantone, and benzoic acid ester derivatives, forexample, ethyl p-dimethylaminobenzoate or ethyl p-diethylaminobenzoate.

Examples of the oxime ester compounds described above include compoundsdescribed in J. C. S. Perkin II, 1653-1660 (1979), J. C. S. Perkin II,156-162 (1979), Journal of Photopolymer Science and Technology, 202-232(1995) and JP-A-2000-66385, and compounds described in JP-A-2000-80068.

The polymerization initiators according to the invention can bepreferably used individually or in combination of two or more thereof.

An amount of the polymerization initiator used in the photosensitivelayer according to the invention is preferably from 0.01 to 20% byweight, more preferably from 0.1 to 15% by weight, and still morepreferably from 1.0 to 10% by weight, based on the total solid contentof the photosensitive layer.

(C) Polymerizable Compound

The polymerizable compound for use in the photosensitive layer accordingto the invention is an addition-polymerizable compound having at leastone ethylenically unsaturated double bond, and it is selected fromcompounds having at least one, preferably two or more, terminalethylenically unsaturated double bonds. Such compounds are widely knownin the art and they can be used in the invention without any particularlimitation. The compound has a chemical form, for example, a monomer, aprepolymer, specifically, a dimer, a trimer or an oligomer, or acopolymer thereof, or a mixture thereof. Examples of the monomer andcopolymer thereof include unsaturated carboxylic acids (for example,acrylic acid, methacrylic acid, itaconic acid, crotonic acid,isocrotonic acid or maleic acid) and esters or amides thereof.Preferably, esters of an unsaturated carboxylic acid with an aliphaticpolyhydric alcohol compound and amides of an unsaturated carboxylic acidwith an aliphatic polyvalent amine compound are used. An additionreaction product of an unsaturated carboxylic acid ester or amide havinga nucleophilic substituent, for example, a hydroxy group, an amino groupor a mercapto group, with a monofunctional or polyfunctional isocyanateor epoxy compound, or a dehydration condensation reaction product of theunsaturated carboxylic acid ester or amide with a monofunctional orpolyfunctional carboxylic acid is also preferably used. Moreover, anaddition reaction product of an unsaturated carboxylic acid ester oramide having an electrophilic substituent, for example, an isocyanategroup or an epoxy group with a monofunctional or polyfunctional alcohol,amine or thiol, or a substitution reaction product of an unsaturatedcarboxylic acid ester or amide having a releasable substituent, forexample, a halogen atom or a tosyloxy group with a monofunctional orpolyfunctional alcohol, amine or thiol is also preferably used. Inaddition, compounds in which the unsaturated carboxylic acid describedabove is replaced by an unsaturated phosphonic acid, styrene, vinylether or the like can also be used.

Specific examples of the monomer, which is an ester of an aliphaticpolyhydric alcohol compound with an unsaturated carboxylic acid, includeacrylic acid esters, for example, ethylene glycol diacrylate,triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethyleneglycol diacrylate, propylene glycol diacrylate, neopentyl glycoldiacrylate, trimethylolpropane triacrylate, trimethylolpropanetri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanedioldiacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycoldiacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythritol diacrylate,dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitoltetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,tri(acryloyloxyethyl)isocyanurate, isocyanuric acid ethylene oxide (EO)modified triacrylate or polyester acrylate oligomer; methacrylic acidesters, for example, tetramethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, neopentyl glycol dimethacrylate,trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate,hexanediol dimethacrylate, pentaerythritol dimethacrylate,pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate,sorbitol trimethacrylate, sorbitol tetramethacrylate,bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane orbis[p-(methacryloxyethoxy)phenyl]dimethylmethane; itaconic acid esters,for example, ethylene glycol diitaconate, propylene glycol diitaconate,1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethyleneglycol diitaconate, pentaerythritol diitaconate or sorbitoltetraitaconate; crotonic acid esters, for example, ethylene glycoldicrotonate, tetramethylene glycol dicrotonate, pentaerythritoldicrotonate or sorbitol tetracrotonate; isocrotonic acid esters, forexample, ethylene glycol diisocrotonate, pentaerythritol diisocrotonateor sorbitol tetraisocrotonate; and maleic acid esters, for example,ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritoldimaleate and sorbitol tetramaleate.

Other examples of the ester, which can be preferably used, includealiphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231,esters having an aromatic skeleton described in JP-A-59-5240,JP-A-59-5241 and JP-A-2-226149, and esters containing an amino groupdescribed in JP-A-1-165613.

The above-described ester monomers can also be used as a mixture.

Specific examples of the monomer, which is an amide of an aliphaticpolyvalent amine compound with an unsaturated carboxylic acid, includemethylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylenebisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriaminetrisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide.Other preferred examples of the amide monomer include amides having acyclohexylene structure described in JP-B-54-21726.

Urethane type addition-polymerizable compounds produced using anaddition reaction between an isocyanate and a hydroxy group are alsopreferably used, and specific examples thereof include vinylurethanecompounds having two or more polymerizable vinyl groups per moleculeobtained by adding a vinyl monomer containing a hydroxy grouprepresented by formula (A) shown below to a polyisocyanate compoundhaving two or more isocyanate groups per molecule, described inJP-B-48-41708.CH₂═C(R₄)COOCH₂—CH(R₅)OH  (A)wherein R₄ and R₅ each independently represents H or CH₃.

Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293 andJP-B-2-16765, and urethane compounds having an ethylene oxide skeletondescribed in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 andJP-B-62-39418 are preferably used. Further, a photosensitive compositionhaving remarkably excellent photo-speed can be obtained by using anaddition polymerizable compound having an amino structure or a sulfidestructure in its molecule, described in JP-A-63-277653, JP-A-63-260909and JP-A-1-105238.

Other examples include polyfunctional acrylates and methacrylates, forexample, polyester acrylates and epoxy acrylates obtained by reacting anepoxy resin with (meth)acrylic acid, described in JP-A-48-64183,JP-B-49-43191 and JP-B-52-30490. Specific unsaturated compoundsdescribed in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, andvinylphosphonic acid type compounds described in JP-A-2-25493 can alsobe exemplified. In some cases, structure containing a perfluoroalkylgroup described in JP-A-61-22048 can be preferably used. Moreover,photocurable monomers or oligomers described in Nippon SecchakuKyokaishi (Journal of Japan Adhesion Society), Vol. 20, No. 7, pages 300to 308 (1984) can also be used.

Details of the method of using the polymerizable compound, for example,selection of the structure, individual or combination use or an amountadded, can be appropriately determined in accordance with thecharacteristic design of the final lithographic printing plateprecursor. For instance, the compound is selected from the followingstandpoints.

In view of the sensitivity, a structure having a large content ofunsaturated group per molecule is preferred and in many cases, adifunctional or more functional compound is preferred. Also, in order toincrease the strength of the image area, that is, hardened layer, atrifunctional or more functional compound is preferred. A combinationuse of compounds different in the functional number or in the kind ofpolymerizable group (for example, an acrylic acid ester, a methacrylicacid ester, a styrene compound or a vinyl ether compound) is aneffective method for controlling both the sensitivity and the strength.

The selection and use method of the polymerizable compound are alsoimportant factors for the compatibility and dispersibility with othercomponents (for example, a binder polymer, a polymerization initiator ora coloring agent) in the photosensitive layer. For instance, thecompatibility may be improved in some cases by using the compound of lowpurity or using two or more kinds of the compounds in combination. Aspecific structure may be selected for the purpose of improving anadhesion property to a support, a protective layer or the like describedhereinafter.

The polymerizable compound is used preferably in a range from 5 to 80%by weight, more preferably in a range from 25 to 75% by weight, based onthe total solid content of the photosensitive layer. The polymerizablecompounds may be used individually or in combination of two or morethereof. In the method of using the polymerizable compound, thestructure, blend and amount added can be appropriately selected bytaking account of the degree of polymerization inhibition due to oxygen,resolution, fogging property, change in refractive index, surfacetackiness and the like. Further, depending on the case, a layerconstruction, for example, an undercoat layer or an overcoat layer, anda coating method, may also be considered.

(D) Hydrophobic Binder Polymer

The hydrophobic binder polymer which can be used in the photosensitivelayer according to the invention is preferably a water-insolublepolymer. Further, the hydrophobic binder polymer which can be used inthe invention preferably does not substantially contain an acid group,for example, a carboxy group, a sulfonic acid group or a phosphoric acidgroup. An acid value (acid content per g of polymer, indicated by thechemical equivalent number) of the binder polymer is preferably 0.3meq/g or less, more preferably 0.1 meq/g or less. In the above-describedrange, film strength, water resistance and ink-receptive property of thephotosensitive layer are increased and improvement in printingdurability can be achieved.

Specifically, the hydrophobic binder polymer which can be used in theinvention is preferably insoluble in water or an aqueous solution havinga pH of 10 or more. The solubility (polymer concentration at thesaturation dissolution) of the hydrophobic binder polymer in water or anaqueous solution having a pH of 10 or more is preferably 0.5% by weightor less, more preferably 0.1% by weight or less. The temperature formeasuring the above-described solubility is temperature at plate-makingdevelopment and it is 25° C. herein.

As for the hydrophobic binder polymer, conventionally known hydrophobicbinder polymers preferably having the solubility in the above-describedrange can be used without limitation as long as the performance of thelithographic printing plate of the invention is not impaired, and alinear organic polymer having film-forming property is preferred.

Preferable examples of such a hydrophobic binder polymer include apolymer selected from an acrylic resin, a polyvinyl acetal resin, apolyurethane resin, a polyamide resin, an epoxy resin, a methacrylicresin, a styrene-based resin and a polyester resin. Among these, anacrylic resin is preferred, and a (meth)acrylic acid ester copolymer ismore preferred. More specifically, a copolymer of a (meth)acrylic acidalkyl or aralkyl ester with a (meth)acrylic acid ester containing a—CH₂CH₂O— or —CH₂CH₂NH— unit in R of the ester residue (—COOR) of the(meth)acrylic acid ester is particularly preferred. The alkyl group inthe (meth)acrylic acid alkyl ester is preferably an alkyl group havingfrom 1 to 5 carbon atoms, more preferably a methyl group. Preferredexamples of the (meth)acrylic acid aralkyl ester includebenzyl(meth)acrylate.

The hydrophobic binder polymer can be imparted with a crosslinkingproperty in order to increase the film strength of the image area.

In order to impart the crosslinking property to the binder polymer, acrosslinkable functional group, for example, an ethylenicallyunsaturated bond is introduced into a main chain or side chain of thepolymer. The crosslinkable functional group may be introduced bycopolymerization or a polymer reaction.

The term “crosslinkable group” as used herein means a group capable ofcrosslinking the polymer binder in the process of a radicalpolymerization reaction which is caused in the photosensitive layer,when the lithographic printing plate precursor is exposed to light. Thecrosslinkable group is not particularly restricted as long as it hassuch a function and includes, for example, an ethylenically unsaturatedbonding group, an amino group or an epoxy group as a functional groupcapable of conducting an addition polymerization reaction. Also, afunctional group capable of forming a radical upon irradiation withlight may be used and such a crosslinkable group includes, for example,a thiol group, a halogen atom and an onium salt structure. Among them,the ethylenically unsaturated bonding group is preferable, andfunctional groups represented by formulae (1) to (3) shown below areparticularly preferable.

In formula (1), R¹ to R³ each independently represents a hydrogen atomor a monovalent organic group. R¹ preferably includes, for example, ahydrogen atom or an alkyl group which may have a substituent. Amongthem, a hydrogen atom or a methyl group is preferable because of highradical reactivity. R² and R³ each independently preferably includes,for example, a hydrogen atom, a halogen atom, an amino group, a carboxylgroup, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyanogroup, an alkyl group which may have a substituent, an aryl group whichmay have a substituent, an alkoxy group which may have a substituent, anaryloxy group which may have a substituent, an alkylamino group whichmay have a substituent, an arylamino group which may have a substituent,an alkylsulfonyl group which may have a substituent and an arylsulfonylgroup which may have a substituent. Among them, a hydrogen atom, acarboxyl group, an alkoxycarbonyl group, an alkyl group which may have asubstituent or an aryl group which may have a substituent is preferablebecause of high radical reactivity.

X represents an oxygen atom, a sulfur atom or —N(R¹²)—, and R¹²represents a hydrogen atom or a monovalent organic group. The monovalentorganic group represented by R¹² includes, for example, an alkyl groupwhich may have a substituent. Among them, a hydrogen atom, a methylgroup, an ethyl group or an isopropyl group is preferable because ofhigh radical reactivity.

Examples of the substituent introduced include an alkyl group, analkenyl group, an alkynyl group, an aryl group, an alkoxy group, anaryloxy group, a halogen atom, an amino group, an alkylamino group, anarylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfogroup, a nitro group, a cyano group, an amido group, an alkylsulfonylgroup and an arylsulfonyl group.

In formula (2), R⁴ to R⁸ each independently represents a hydrogen atomor a monovalent organic group. R⁴ to R⁸ each independently preferablyincludes, for example, a hydrogen atom, a halogen atom, an amino group,a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfogroup, a nitro group, a cyano group, an alkyl group which may have asubstituent, an aryl group which may have a substituent, an alkoxy groupwhich may have a substituent, an aryloxy group which may have asubstituent, an alkylamino group which may have a substituent, anarylamino group which may have a substituent, an alkylsulfonyl groupwhich may have a substituent and an arylsulfonyl group which may have asubstituent. Among them, a hydrogen atom, a carboxyl group, analkoxycarbonyl group, an alkyl group which may have a substituent or anaryl group which may have a substituent is preferable.

Examples of the substituent introduced include those described inFormula (1). Y represents an oxygen atom, a sulfur atom or —N(R¹²)—, andR¹² has the same meaning as R¹² defined in Formula (1). Preferredexamples for R¹² are also same as those described in Formula (1).

In formula (3), R⁹ preferably represents a hydrogen atom or an alkylgroup which may have a substituent. Among them, a hydrogen atom or amethyl group is preferable because of high radical reactivity. R¹⁰ andR¹¹ each independently represents, for example, a hydrogen atom, ahalogen atom, an amino group, a dialkylamino group, a carboxyl group, analkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, analkyl group which may have a substituent, an aryl group which may have asubstituent, an alkoxy group which may have a substituent, an aryloxygroup which may have a substituent, an alkylamino group which may have asubstituent, an arylamino group which may have a substituent, analkylsulfonyl group which may have a substituent and an arylsulfonylgroup which may have a substituent. Among them, a hydrogen atom, acarboxyl group, an alkoxycarbonyl group, an alkyl group which may have asubstituent or an aryl group which may have a substituent is preferablebecause of high radical reactivity.

Examples of the substituent introduced include those described inFormula (1). Z represents an oxygen atom, a sulfur atom, —N(R¹³)— or aphenylene group which may have a substituent. R¹³ includes an alkylgroup which may have a substituent or the like. Among them, a methylgroup, an ethyl group or an isopropyl group is preferable because ofhigh radical reactivity.

Among the polymers, a (meth)acrylic acid copolymer and a polyurethaneeach having a crosslinkable group in the side chain thereof are morepreferable.

In the hydrophobic binder polymer having a crosslinking property, forexample, a free radical (a polymerization initiating radical or apropagating radical in the process of polymerization of thepolymerizable compound) is added to the crosslinkable functional groupto cause an addition-polymerization between polymers directly or througha polymerization chain of the polymerizable compound, as a result,crosslinking is formed between polymer molecules to effect curing.Alternatively, an atom (for example, a hydrogen atom on the carbon atomadjacent to the functional crosslinkable group) in the polymer iswithdrawn by a free radical to produce a polymer radical and the polymerradicals combine with each other to form crosslinking between polymermolecules to effect curing.

The content of the crosslinkable group (content of radical-polymerizableunsaturated double bond determined by iodine titration) in thehydrophobic binder polymer is preferably from 0.1 to 10.0 mmol, morepreferably from 1.0 to 7.0 mmol, and most preferably from 2.0 to 5.5mmol, per g of the hydrophobic binder polymer.

In view of improvement in the developing property with an aqueoussolution, the binder polymer is preferably hydrophilic. On the otherhand, in view of increasing the printing durability, it is importantthat the binder polymer has good compatibility with the polymerizablecompound contained in the photosensitive layer, that is, the binderpolymer is preferably oleophilic. From these standpoints, it is alsoeffective in the invention to copolymerize a hydrophilicgroup-containing component and an oleophilic group-containing componentin the hydrophobic binder polymer in order to improve the developingproperty and the printing durability. Examples of the hydrophilicgroup-containing component which can be preferably used include thosehaving a hydrophilic group, for example, a hydroxy group, a carboxylategroup, a hydroxyethyl group, an ethyleneoxy group, a hydroxypropylgroup, a polyoxyethyl group, a polyoxypropyl group, an amino group, anaminoethyl group, an aminopropyl group, an ammonium group, an amidogroup and a carboxymethyl group.

The hydrophobic binder polymer preferably has a weight average molecularweight of 5,000 or more, more preferably from 10,000 to 300,000, and anumber average molecular weight of 1,000 or more, more preferably from2,000 to 250,000. The polydispersity (weight average molecularweight/number average molecular weight) is preferably from 1.1 to 10.

The hydrophobic binder polymer may be any of a random polymer, a blockpolymer, a graft polymer and the like, and it is preferably a randompolymer.

The hydrophobic binder polymers may be used individually or incombination of two or more thereof.

From the standpoint of preferable strength of the image area and goodimage-forming property, the content of the hydrophobic binder polymer isfrom 5 to 90% by weight, preferably from 10 to 70% by weight, morepreferably from 10 to 60% by weight, based on the total solid content ofthe photosensitive layer.

(E) Chain Transfer Agent

It is preferred to incorporate a chain transfer agent into thephotosensitive layer according to the invention. The chain transferagent contributes to improvements in the sensitivity and preservationstability. Compounds which function as the chain transfer agentsinclude, for example, compounds containing SH, PH, SiH or GeH in theirmolecules. Such a compound donates hydrogen to a radical species of lowactivity to generate a radical, or is oxidized and then deprotonated togenerate a radical.

In the photosensitive layer according to the invention, a thiol compound(for example, a 2-mercaptobenzimidazole) is particularly preferably usedas the chain transfer agent.

Among them, a thiol compound represented by formula (T) shown below isparticularly preferably used. By using the thiol compound represented byformula (T) as the chain transfer agent, a problem of the odor anddecrease in sensitivity due to evaporation of the compound from thephotosensitive layer or diffusion thereof into other layers are avoidedand a lithographic printing plate precursor which is excellent inpreservation stability and exhibits high sensitivity and good printingdurability is obtained.

In formula (T), R represents an alkyl group which may have a substituentor an aryl group which may have a substituent; and A represents anatomic group necessary for forming a 5-membered or 6-membered heteroring containing a carbon atom together with the N═C—N linkage, and A mayhave a substituent.

Compounds represented by formulae (T-1) and (T-2) shown below are morepreferably used.

In formulae (T-1) and (T-2), R represents an alkyl group which may havea substituent or an aryl group which may have a substituent; and Xrepresents a halogen atom, an alkoxy group which may have a substituent,an alkyl group which may have a substituent or an aryl group which mayhave a substituent.

Specific examples of the compound represented by formula (T) are setforth below, but the invention should not be construed as being limitedthereto.

An amount of the chain transfer agent (for example, the thiol compound)used is preferably from 0.01 to 20% by weight, more preferably from 0.1to 15% by weight, and still more preferably from 1.0 to 10% by weight,based on the total solid content of the photosensitive layer.

(F) Co-Sensitizer

In the invention, a co-sensitizer may be used. The co-sensitizer is anadditive capable of further increasing the sensitivity of thephotosensitive layer, when it is added to the photosensitive layer. Theoperation mechanism of the co-sensitizer is not quite clear but may beconsidered to be mostly based on the following chemical process.Specifically, the co-sensitizer reacts with various intermediate activespecies (for example, a radical, a peroxide, an oxidizing agent or areducing agent) generated during the process of photo-reaction initiatedby the photopolymerization initiation system and subsequentaddition-polymerization reaction to produce new active radicals. Theco-sensitizers are roughly classified into (a) a compound which isreduced to produce an active radical, (b) a compound which is oxidizedto produce an active radical and (c) a compound which reacts with aradical having low activity to convert it into a more highly activeradical or acts as a chain transfer agent. However, in many cases, acommon view about that an individual compound belongs to which type isnot present.

(a) Compound which is Reduced to Produce an Active Radical

Compound having Carbon-Halogen Bond:

An active radical is considered to be generated by the reductivecleavage of the carbon-halogen bond. Specific examples of the compoundpreferably used include a trihalomethyl-s-triazine and atrihalomethyloxadiazole.

Compound having Nitrogen-Nitrogen Bond:

An active radical is considered to be generated by the reductivecleavage of the nitrogen-nitrogen bond. Specific examples of thecompound preferably used include a hexaarylbiimidazole.

Compound having Oxygen-Oxygen Bond:

An active radical is considered to be generated by the reductivecleavage of the oxygen-oxygen bond. Specific examples of the compoundpreferably used include an organic peroxide.

Onium Compound:

An active radical is considered to be generated by the reductivecleavage of a carbon-hetero bond or oxygen-nitrogen bond. Specificexamples of the compound preferably used include a diaryliodonium salt,a triarylsulfonium salt and an N-alkoxypyridinium (azinium) salt.

(b) Compound which is Oxidized to Produce an Active Radical

Alkylate Complex:

An active radical is considered to be generated by the oxidativecleavage of a carbon-hetero bond. Specific examples of the compoundpreferably used include a triaryl alkyl borate.

Alkylamine Compound:

An active radical is considered to be generated by the oxidativecleavage of a C—X bond on the carbon adjacent to nitrogen, wherein X ispreferably, for example, a hydrogen atom, a carboxyl group, atrimethylsilyl group or a benzyl group. Specific examples of thecompound include an ethanolamine, an N-phenylglycine and anN-trimethylsilylmethylaniline.

Sulfur-Containing or Tin-Containing Compound:

A compound in which the nitrogen atom of the above-described amine isreplaced by a sulfur atom or a tin atom is considered to generate anactive radical in the same manner. Also, a compound having an S—S bondis known to effect sensitization by the cleavage of the S—S bond.

α-Substituted Methylcarbonyl Compound:

An active radical can be generated by the oxidative cleavage ofcarbonyl-α-carbon bond. The compound in which the carbonyl is convertedinto an oxime ether also shows the similar function. Specific examplesof the compound include an2-alkyl-1-[4-(alkylthio)phenyl]-2-morpholinopronone-1, an oxime etherobtained by a reaction of the2-alkyl-1-[4-(alkylthio)phenyl]-2-morpholinopronone-1 with ahydroxyamine and subsequent etherification of the N—OH and an oximeester obtained by a reaction of the2-alkyl-1-[4-(alkylthio)phenyl]-2-morpholinopronone-1 with ahydroxyamine and subsequent esterification of the N—OH.

Sulfinic Acid Salt:

An active radical can be reductively generated. Specific examples of thecompound include sodium arylsulfinate.

(c) Compound which Reacts with a Radical to Convert it into a MoreHighly Active Radical or Acts as a Chain Transfer Agent:

For example, a compound having SH, PH, SiH or GeH in its molecule isused as the compound which reacts with a radical to convert it into amore highly active radical or acts as a chain transfer agent. Thecompound donates hydrogen to a low active radical species to generate aradical or is oxidized and deprotonized to generate a radical. Specificexamples of the compound include a 2-mercaptobenzimidazole.

Specific examples of the co-sensitizer include compounds described inJP-A-9-236913 as additives for the purpose of increasing sensitivity.Some of them are set forth below, but the invention should not beconstrued as being limited thereto.

Similarly to the above-described sensitizing dye, the co-sensitizer canbe subjected to various chemical modifications so as to improve thecharacteristics of the photosensitive layer of the lithographic printingplate precursor. For instance, methods, for example, binding to thesensitizing dye, polymerization initiator, addition-polymerizableunsaturated compound or other radical-generating part, introduction of ahydrophilic site, introduction of a substituent for improvingcompatibility or inhibiting deposition of crystal, introduction of asubstituent for improving adhesion, and formation of a polymer, may beused. The co-sensitizers may be used individually or in combination oftwo or more thereof. The amount of the co-sensitizer used is ordinarilyfrom 0.05 to 100 parts by weight, preferably from 1 to 80 parts byweight, and more preferably from 3 to 50 parts by weight, per 100 partsby weight of the polymerizable compound having an ethylenicallyunsaturated double bond.

<Microcapsule>

In the invention, in order to incorporate the above-describedconstituting components of the photosensitive layer and otherconstituting components described hereinafter into the photosensitivelayer, a part or whole of the constituting components is encapsulatedinto microcapsules and added to the photosensitive layer as described,for example, in JP-A-2001-277740 and JP-A-2001-277742. In such a case,each constituting component may be present inside or outside themicrocapsule in an appropriate ratio.

As a method of microencapsulating the constituting components of thephotosensitive layer, known methods can be used. Methods for theproduction of microcapsules include, for example, a method of utilizingcoacervation described in U.S. Pat. Nos. 2,800,457 and 2,800,458, amethod of using interfacial polymerization described in U.S. Pat. No.3,287,154, JP-B-38-19574 and JP-B-42-446, a method of using depositionof polymer described in U.S. Pat. Nos. 3,418,250 and 3,660,304, a methodof using an isocyanate polyol wall material described in U.S. Pat. No.3,796,669, a method of using an isocyanate wall material described inU.S. Pat. No. 3,914,511, a method of using a urea-formaldehyde-type orurea-formaldehyde-resorcinol-type wall-forming material described inU.S. Pat. Nos. 4,001,140, 4,087,376 and 4,089,802, a method of using awall material, for example, a melamine-formaldehyde resin orhydroxycellulose described in U.S. Pat. No. 4,025,445, an in-situ methodby polymerization of monomer described in JP-B-36-9163 and JP-B-51-9079,a spray drying method described in British Patent 930,422 and U.S. Pat.No. 3,111,407, and an electrolytic dispersion cooling method describedin British Patents 952,807 and 967,074, but the invention should not beconstrued as being limited thereto.

A preferable microcapsule wall used in the invention hasthree-dimensional crosslinking and has a solvent-swellable property.From this point of view, a preferable wall material of the microcapsuleincludes polyurea, polyurethane, polyester, polycarbonate, polyamide anda mixture thereof, and particularly polyurea and polyurethane arepreferred. Further, a compound having a crosslinkable functional group,for example, an ethylenically unsaturated bond, capable of beingintroduced into the hydrophobic binder polymer described above may beintroduced into the microcapsule wall.

An average particle size of the microcapsule is preferably from 0.01 to3.0 μm, more preferably from 0.05 to 2.0 μm, and particularly preferablyfrom 0.10 to 1.0 μm. In the above-described range, preferable resolutionand good preservation stability can be achieved.

<Other Constituting Components of Photosensitive Layer>

Into the photosensitive layer according to the invention, variousadditives can further be incorporated, if desired. Such additives aredescribed in detail below.

<Surfactant>

In the invention, it is preferred to use a surfactant in thephotosensitive layer in order to progress the developing property and toimprove the state of surface coated. The surfactant includes, forexample, a nonionic surfactant, an anionic surfactant, a cationicsurfactant, an amphoteric surfactant and a fluorine-based surfactant.The surfactants may be used individually or in combination of two ormore thereof.

The nonionic surfactant used in the invention is not particularrestricted, and nonionic surfactants hitherto known can be used.Examples of the nonionic surfactant include polyoxyethylene alkylethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerinfatty acid partial esters, sorbitan fatty acid partial esters,pentaerythritol fatty acid partial esters, propylene glycol monofattyacid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitanfatty acid partial esters, polyoxyethylene sorbitol fatty acid partialesters, polyethylene glycol fatty acid esters, polyglycerol fatty acidpartial esters, polyoxyethylenated castor oils, polyoxyethylene glycerolfatty acid partial esters, fatty acid diethanolamides,N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines,triethanolamine fatty acid esters, trialylamine oxides, polyethyleneglycols, and copolymers of polyethylene glycol and polypropylene glycol.

The anionic surfactant used in the invention is not particularlyrestricted and anionic surfactants hitherto known can be used. Examplesof the anionic surfactant include fatty acid salts, abietic acid salts,hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,dialkylsulfosuccinic ester salts, straight-chain alkylbenzenesulfonicacid salts, branched alkylbenzenesulfonic acid salts,alkylnaphthalenesulfonic acid salts, alkylphenoxypolyoxy ethylenepropylsulfonic acid salts, polyoxyethylene alkylsulfophenyl ether salts,N-methyl-N-oleyltaurine sodium salt, N-alkylsulfosuccinic monoamidedisodium salts, petroleum sulfonic acid salts, sulfated beef tallow oil,sulfate ester slats of fatty acid alkyl ester, alkyl sulfate estersalts, polyoxyethylene alkyl ether sulfate ester salts, fatty acidmonoglyceride sulfate ester salts, polyoxyethylene alkyl phenyl ethersulfate ester salts, polyoxyethylene styrylphenyl ether sulfate estersalts, alkyl phosphate ester salts, polyoxyethylene alkyl etherphosphate ester salts, polyoxyethylene alkyl phenyl ether phosphateester salts, partial saponification products of styrene/maleic anhydridecopolymer, partial saponification products of olefin/maleic anhydridecopolymer and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the invention is not particularlyrestricted and cationic surfactants hitherto known can be used. Examplesof the cationic surfactant include alkylamine salts, quaternary ammoniumsalts, polyoxyethylene alkyl amine salts and polyethylene polyaminederivatives.

The amphoteric surfactant used in the invention is not particularlyrestricted and amphoteric surfactants hitherto known can be used.Examples of the amphoteric surfactant include carboxybetaines,aminocarboxylic acids, sulfobetaines, aminosulfuric esters andimidazolines.

In the surfactants described above, the term “polyoxyethylene” can bereplaced with “polyoxyalkylene”, for example, polyoxymethylene,polyoxypropylene or polyoxybutylene, and such surfactants can also beused in the invention.

Further, a preferred surfactant includes a fluorine-based surfactantcontaining a perfluoroalkyl group in its molecule. Examples of thefluorine-based surfactant include an anionic type, for example,perfluoroalkyl carboxylates, perfluoroalkyl sulfonates orperfluoroalkylphosphates; an amphoteric type, for example,perfluoroalkyl betaines; a cationic type, for example, perfluoroalkyltrimethyl ammonium salts; and a nonionic type, for example,perfluoroalkyl amine oxides, perfluoroalkyl ethylene oxide adducts,oligomers having a perfluoroalkyl group and a hydrophilic group,oligomers having a perfluoroalkyl group and an oleophilic group,oligomers having a perfluoroalkyl group, a hydrophilic group and anoleophilic group or urethanes having a perfluoroalkyl group and anoleophilic group. Further, fluorine-based surfactants described inJP-A-62-170950, JP-A-62-226143 and JP-A-60-168144 are also preferablyexemplified.

The surfactants may be used individually or in combination of two ormore thereof.

A content of the surfactant is preferably from 0.001 to 10% by weight,more preferably from 0.01 to 7% by weight, based on the total solidcontent of the photosensitive layer.

<Hydrophilic Polymer>

In the invention, a hydrophilic polymer may be incorporated into thephotosensitive layer in order to improve the developing property anddispersion stability of microcapsule.

Preferable examples of the hydrophilic polymer include those having ahydrophilic group, for example, a hydroxy group, a carboxyl group, acarboxylate group, a hydroxyethyl group, a polyoxyethyl group, ahydroxypropyl group, a polyoxypropyl group, an amino group, anaminoethyl group, an aminopropyl group, an ammonium group, an amidogroup, a carboxymethyl group, a sulfonic acid group and a phosphoricacid group.

Specific examples of the hydrophilic polymer include gum arabic, casein,gelatin, a starch derivative, carboxymethyl cellulose or a sodium saltthereof, cellulose acetate, sodium alginate, a vinyl acetate-maleic acidcopolymer, a styrene-maleic acid copolymer, polyacrylic acid or a saltthereof, polymethacrylic acid or a salt thereof, a homopolymer orcopolymer of hydroxyethyl methacrylate, a homopolymer or copolymer ofhydroxyethyl acrylate, a homopolymer or copolymer of hydroxypropylmethacrylate, a homopolymer or copolymer of hydroxypropyl acrylate, ahomopolymer or copolymer of hydroxybutyl methacrylate, a homopolymer orcopolymer of hydroxybutyl acrylate, polyethylene glycol, ahydroxypropylene polymer, polyvinyl alcohol, a hydrolyzed polyvinylacetate having a hydrolysis degree of 60% by mole or more, preferably80% by mole or more, polyvinyl formal, polyvinyl butyral,polyvinylpyrrolidone, a homopolymer or polymer of acrylamide, ahomopolymer or copolymer of methacrylamide, a homopolymer or copolymerof N-methylolacrylamide, polyvinylpyrrolidone, an alcohol-soluble nylon,and a polyether of 2,2-bis(4-hydroxyphenyl)propane with epichlorohydrin.

The hydrophilic polymer preferably has a weight average molecular weightof 5,000 or more, more preferably from 10,000 to 300,000. Thehydrophilic polymer may be any of a random polymer, a block polymer, agraft polymer or the like.

The content of the hydrophilic polymer in the photosensitive layer ispreferably 20% by weight or less, more preferably 10% by weight or less,based on the total solid content of the photosensitive layer.

<Coloring Agent>

In the invention, a dye having large absorption in the visible lightregion can be used as a coloring agent for the image. Specific examplesthereof include Oil Yellow #101, Oil Yellow #103, Oil Pink #312, OilGreen BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, OilBlack T-505 (all produced by Orient Chemical Industry Co., Ltd.),Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535),Ethyl Violet, Rhodamine B (CI45170B), Malachite Green (CI42000),Methylene Blue (CI52015), and dyes described in JP-A-62-293247. Also, apigment, for example, phthalocyanine-based pigment, azo-based pigment,carbon black and titanium oxide can be preferably used.

It is preferable to add the coloring agent, because the image area andthe non-image area after the image formation can be easilydistinguished. The amount of the coloring agent added is preferably from0.01 to 10% by weight based on the total solid content of thephotosensitive layer.

<Print-Out Agent>

In the photosensitive layer according to the invention, a compoundcapable of undergoing discoloration by the effect of an acid or aradical can be added in order to form a print-out image. As such acompound, for example, various dyes, e.g., diphenylmethane-based,triphenylmethane-based, thiazine-based, oxazine-based, xanthene-based,anthraquinone-based, iminoquinone-based, azo-based and azomethine-baseddyes are effectively used.

Specific examples thereof include dyes, for example, Brilliant Green,Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuchsine, MethylViolet 2B, Quinaldine Red, Rose Bengale, Metanil Yellow,Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Paramethyl Red, CongoRed, Benzopurpurine 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A,Methyl Violet, Malachite Green, Parafuchsine, Victoria Pure Blue BOH(produced by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (produced byOrient Chemical Industry Co., Ltd.), Oil Pink #312 (produced by OrientChemical Industry Co., Ltd.), Oil Red 5B (produced by Orient ChemicalIndustry Co., Ltd.), Oil Scarlet #308 (produced by Orient ChemicalIndustry Co., Ltd.), Oil Red OG (produced by Orient Chemical IndustryCo., Ltd.), Oil Red RR (produced by Orient Chemical Industry Co., Ltd.),Oil Green #502 (produced by Orient Chemical Industry Co., Ltd.), SpironRed BEH Special (produced by Hodogaya Chemical Co., Ltd.), m-CresolPurple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine B,Auramine, 4-p-diethyl-aminophenyliminonaphthoquinone,2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone,2-carboxystearyl-amino-4-p-N,N-bis(hydroxyethyl)aminophenyliminonaphthoquinone,1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone, and leuco dyes,for example, p,p′,p″-hexamethyltriaminotriphenyl methane (leuco CrystalViolet) and Pergascript Blue SRB (produced by Ciba Geigy).

Other preferable examples include leuco dyes known as a material forheat-sensitive paper or pressure-sensitive paper. Specific examplesthereof include Crystal Violet Lactone, Malachite Green Lactone, BenzoylLeuco Methylene Blue,2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane,2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane,3,6-dimethoxyfluorane,3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane,3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane,3-(N,N-diethylamino)-6-methyl-7-anilinofluorane,3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane,3-(N,N-diethylamino)-6-methyl-7-chlorofluorane,3-(N,N-diethylamino)-6-methoxy-7-aminofluorane,3-(N,N-diethylamino)-7-(4-chloroanilino)fluorane,3-(N,N-diethylamino)-7-chlorofluorane,3-(N,N-diethylamino)-7-benzylaminofluorane,3-(N,N-diethylamino)-7,8-benzofluorane,3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane,3-(N,N-dibutylamino)-6-methyl-7-xylidinofluorane,3-piperidino-6-methyl-7-anilinofluorane,3-pyrrolidino-6-methyl-7-anilinofluorane,3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide,3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide,3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalideand 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide.

The dye capable of undergoing discoloration by the effect of an acid ora radical is preferably added in an amount of 0.01 to 15% by weightbased on the total solid content of the photosensitive layer.

<Polymerization Inhibitor>

In the photosensitive layer according to the invention, a small amountof a thermal polymerization inhibitor is preferably added in order toprevent the radical polymerizable compound from undergoing undesirablethermal polymerization during the preparation or preservation of thephotosensitive layer.

Preferable examples of the thermal polymerization inhibitor includehydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol,tert-butyl catechol, benzoquinone,4,4′-thiobis(3-methyl-6-tert-butylphenol),2,2′-methylenebis(4-methyl-6-tert-butylphenol) andN-nitroso-N-phenylhydroxylamine aluminum salt.

The amount of the thermal polymerization inhibitor added is preferablyfrom about 0.01 to about 5% by weight based on the total solid contentof the photosensitive layer.

<Higher Fatty Acid Derivative>

In the photosensitive layer according to the invention, for example, ahigher fatty acid derivative, e.g., behenic acid or behenic acid amidemay be added and localized on the surface of the photosensitive layerduring the process of drying after coating in order to avoidpolymerization inhibition due to oxygen. The amount of the higher fattyacid derivative added is preferably from about 0.1 to about 10% byweight based on the total solid content of the photosensitive layer.

<Plasticizer>

The photosensitive layer according to the invention may contain aplasticizer. Preferable examples of the plasticizer include a phthalicacid ester, for example, dimethyl phthalate, diethyl phthalate, dibutylphthalate, diisobutyl phthalate, diocyl phthalate, octyl caprylphthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzylphthalate, diisodecyl phthalate or diallyl phthalate; a glycol ester,for example, dimethyl glycol phthalate, ethyl phthalylethyl glycolate,methyl phthalylethyl glycolate, butyl phthalylbutyl glycolate ortriethylene glycol dicaprylic acid ester; a phosphoric acid ester, forexample, tricresyl phosphate or triphenyl phosphate; an aliphaticdibasic acid ester, for example, diisobutyl adipate, dioctyl adipate,dimethyl sebacate, dibutyl sebacate, dioctyl azelate or dibutyl maleate;polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl esterand butyl laurate. The content of the plasticizer is preferably about30% by weight or less based on the total solid content of thephotosensitive layer.

<Fine Inorganic Particle>

The photosensitive layer according to the invention may contain fineinorganic particle in order to increase strength of the hardened layerin the image area. The fine inorganic particle preferably includes, forexample, silica, alumina, magnesium oxide, titanium oxide, magnesiumcarbonate, calcium alginate and a mixture thereof. Even if the fineinorganic particle has no light to heat converting property, it can beused, for example, for strengthening the layer or enhancing interfaceadhesion property due to surface roughening. The fine inorganic particlepreferably has an average particle size from 5 nm to 10 μm and morepreferably from 0.5 to 3 μm. In the above-described range, it is stablydispersed in the photosensitive layer, sufficiently maintains the filmstrength of the photosensitive layer and can form the non-image areaexcellent in hydrophilicity and preventing from stain at the printing.

The fine inorganic particle described above is easily available as acommercial product, for example, colloidal silica dispersion.

The content of the fine inorganic particle is preferably 20% by weightor less, and more preferably 10% by weight or less based on the totalsolid content of the photosensitive layer.

<Hydrophilic Low Molecular Weight Compound>

The photosensitive layer according to the invention may contain ahydrophilic low molecular weight compound in order to improve thedeveloping property. The hydrophilic low molecular weight compoundincludes a water-soluble organic compound, for example, a glycolcompound, e.g., ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol or tripropylene glycol, or an etheror ester derivative thereof, a polyhydroxy compound, e.g., glycerine orpentaerythritol, an organic amine, e.g., triethanol amine, diethanolamine or monoethanol amine, or a salt thereof, an organic sulfonic acid,e.g., toluene sulfonic acid or benzene sulfonic acid, or a salt thereof,an organic phosphonic acid, e.g., phenyl phosphonic acid, or a saltthereof, an organic carboxylic acid, e.g., tartaric acid, oxalic acid,citric acid, maleic acid, lactic acid, gluconic acid or an amino acid,or a salt thereof, and an organic quaternary ammonium salt, e.g.,tetraethyl ammonium hydrochloride.

<Formation of Photosensitive Layer>

The photosensitive layer according to the invention is formed bydispersing or dissolving each of the necessary constituting componentsdescribed above to prepare a coating solution and coating the solution.The solvent used include, for example, ethylene dichloride,cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol,ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methxyethylacetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate,ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide,tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane,γ-butyrolactone, toluene and water, but the invention should not beconstrued as being limited thereto. The solvents may be usedindividually or as a mixture. The solid concentration of the coatingsolution is preferably from 1 to 50% by weight.

The photosensitive layer according to the invention may also be formedby preparing plural coating solutions by dispersing or dissolving thesame or different components described above into the same or differentsolvents and conducting repeatedly plural coating and drying.

The coating amount (solid content) of the photosensitive layer on thesupport after the coating and drying may be varied depending on the use,but ordinarily, it is preferably from 0.3 to 3.0 g/m². In theabove-described range, the preferable sensitivity and good film propertyof the photosensitive layer can be obtained.

Various methods can be used for the coating. Examples of the methodinclude bar coater coating, spin coating, spray coating, curtaincoating, dip coating, air knife coating, blade coating and roll coating.

(Protective Layer)

In the lithographic printing plate precursor according to the invention,a protective layer (oxygen-blocking layer) is preferably provided on thephotosensitive layer in order to prevent diffusion and penetration ofoxygen which inhibits the polymerization reaction at the time ofexposure. The protective layer for use in the invention preferably hasoxygen permeability (A) at 25° C. under one atmosphere of 1.0≦(A)≦20(ml/m²·day). When the oxygen permeability (A) is extremely lower than1.0 (ml/m²·day), problems may occur in that an undesirablepolymerization reaction arises during the production or preservationbefore image exposure and in that undesirable fog or spread of imageline occurs at the image exposure. On the contrary, when the oxygenpermeability (A) greatly exceeds 20 (ml/m²·day), decrease in sensitivitymay be incurred. The oxygen permeability (A) is more preferably in arange of 1.5≦(A)≦12 (ml/m²·day), and still more preferably in a range of2.0≦(A)≦10.0 (ml/m²·day). Besides the above described oxygenpermeability, as for the characteristics required of the protectivelayer, it is desired that the protective layer does not substantiallyhinder the transmission of light for the exposure, is excellent inadhesion to the photosensitive layer, and can be easily removed during adevelopment step after the exposure. Contrivances on the protectivelayer have been heretofore made and described in detail in U.S. Pat. No.3,458,311 and JP-B-55-49729.

As the material of the protective layer, a water-soluble polymercompound relatively excellent in crystallizability is preferably used.Specifically, a water-soluble polymer, for example, polyvinyl alcohol,vinyl alcohol/vinyl phthalate copolymer, vinyl acetate/vinylalcohol/vinyl phthalate copolymer, vinyl acetate/crotonic acidcopolymer, polyvinyl pyrrolidone, acidic cellulose, gelatin, gum arabic,polyacrylic acid or polyacrylamide is enumerated. The water-solublepolymer compounds may be used individually or as a mixture. Of thecompounds, when polyvinyl alcohol is used as a main component, the bestresults can be obtained in the fundamental characteristics, for example,oxygen-blocking property and removability of the protective layer bydevelopment.

Polyvinyl alcohol for use in the protective layer may be partiallysubstituted with ester, ether or acetal as long as it containsunsubstituted vinyl alcohol units for achieving the necessaryoxygen-blocking property and water solubility. Also, a part of polyvinylalcohol may have other copolymer component. As specific examples ofpolyvinyl alcohol, those having a hydrolyzing rate of 71 to 100% and apolymerization repeating unit number of 300 to 2,400 are exemplified.Specific examples thereof include PVA-105, PVA-110, PVA-117, PVA-117H,PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204,PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E,PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613 and L-8 (produced byKuraray Co., Ltd.). They can be used individually or as a mixture.According to a preferred embodiment, the content of polyvinyl alcohol inthe protective layer is from 20 to 95% by weight, more preferably from30 to 90% by weight.

Also, known modified polyvinyl alcohol can be preferably used. Forinstance, polyvinyl alcohols of various polymerization degrees having atrandom a various kind of hydrophilic modified cites, for example, ananion-modified cite modified with an anion, e.g., a carboxyl group or asulfo group, a cation-modified cite modified with a cation, e.g., anamino group or an ammonium group, a silanol-modified cite or athiol-modified cite, and polyvinyl alcohols of various polymerizationdegrees having at the terminal of the polymer a various kind of modifiedcites, for example, the above-described anion-modified cite, cationmodified cite, silanol-modified cite or thiol-modified cite, analkoxy-modified cite, a sulfide-modified cite, an ester modified cite ofvinyl alcohol with a various kind of organic acids, an ester modifiedcite of the above-described anion-modified cite with an alcohol or anepoxy-modified cite are exemplified.

As a component used as a mixture with polyvinyl alcohol, polyvinylpyrrolidone or a modified product thereof is preferable from theviewpoint of the oxygen-blocking property and removability bydevelopment. The content thereof is ordinarily from 3.5 to 80% byweight, preferably from 10 to 60% by weight, and more preferably from 15to 30% by weight, in the protective layer.

The components of the protective layer (selection of PVA and use ofadditives) and the coating amount are determined taking intoconsideration fogging property, adhesion property and scratch resistancebesides the oxygen-blocking property and removability by development. Ingeneral, the higher the hydrolyzing rate of the PVA used (the higher theunsubstituted vinyl alcohol unit content in the protective layer) andthe larger the layer thickness, the higher is the oxygen-blockingproperty, thus it is advantageous in the point of sensitivity. Themolecular weight of the (co)polymer, for example, polyvinyl alcohol(PVA) is ordinarily from 2,000 to 10,000,000, and preferably from 20,000to 3,000,000.

As other additive of the protective layer, glycerin, dipropylene glycolor the like can be added in an amount corresponding to several % byweight of the (co)polymer to provide flexibility. Further, an anionicsurfactant, for example, sodium alkylsulfate or sodium alkylsulfonate;an amphoteric surfactant, for example, alkylaminocarboxylate andalkylaminodicarboxylate; or a nonionic surfactant, for example,polyoxyethylene alkyl phenyl ether can be added in an amountcorresponding to several % by weight of the (co)polymer.

The adhesion property of the protective layer to the photosensitivelayer and scratch resistance are also extremely important in view ofhandling of the printing plate precursor. Specifically, when ahydrophilic layer comprising a water-soluble polymer is laminated on aoleophilic photosensitive layer, layer peeling due to insufficientadhesion is liable to occur, and the peeled portion causes such a defectas failure in hardening of the photosensitive layer due topolymerization inhibition by oxygen. Various proposals have been madefor improving the adhesion between the photosensitive layer and theprotective layer. For example, it is described in U.S. patentapplication Ser. Nos. 292,501 and 44,563 that a sufficient adhesionproperty can be obtained by mixing from 20 to 60% by weight of anacryl-based emulsion or a water-insoluble vinyl pyrrolidone/vinylacetate copolymer with a hydrophilic polymer mainly comprising polyvinylalcohol and laminating the resulting mixture on the photosensitivelayer. Any of these known techniques can be applied to the protectivelayer according to the invention. Coating methods of the protectivelayer are described in detail, for example, in U.S. Pat. No. 3,458,311and JP-B-55-49729.

Further, it is also preferred to incorporate an inorganic stratiformcompound into the protective layer of the lithographic printing plateprecursor according to the invention for the purpose of improving theoxygen-blocking property and property for protecting the surface ofphotosensitive layer.

The inorganic stratiform compound used here is a particle having a thintabular shape and includes, for instance, mica, for example, naturalmica represented by the following formula: A (B, C)₂₋₅ D₄ O₁₀ (OH, F,O)₂, (wherein A represents any one of K, Na and Ca, B and C eachrepresents any one of Fe (II), Fe (III), Mn, Al, Mg and V, and Drepresents Si or Al) or synthetic mica; talc represented by thefollowing formula: 3MgO.4SiO.H₂O; teniolite; montmorillonite; saponite;hectolite; and zirconium phosphate.

Of the micas, examples of the natural mica include muscovite,paragonite, phlogopite, biotite and lepidolite. Examples of thesynthetic mica include non-swellable mica, for example, fluorphlogopiteKMg₃(AlSi₃O₁₀)F₂ or potassium tetrasilic mica KMg_(2.5)(Si₄O₁₀)F₂, andswellable mica, for example, Na tetrasilic mica NaMg_(2.5)(Si₄O₁₀)F₂, Naor Li teniolite (Na, Li)Mg₂Li(Si₄O₁₀)F₂, or montmorillonite based Na orLi hectolite (Na, Li)_(1/8)Mg_(2/5)Li_(1/8)(Si₄O₁₀)F₂. Syntheticsmectite is also useful.

Of the inorganic stratiform compounds, fluorine based swellable mica,which is a synthetic inorganic stratiform compound, is particularlyuseful in the invention. Specifically, the swellable synthetic mica andan swellable clay mineral, for example, montmorillonite, saponite,hectolite or bentonite have a stratiform structure comprising a unitcrystal lattice layer having thickness of approximately 10 to 15angstroms, and metallic atom substitution in the lattices thereof isremarkably large in comparison with other clay minerals. As a result,the lattice layer results in lack of positive charge and to compensateit, a cation, for example, Na⁺, Ca²⁺ or Mg²⁺, is adsorbed between thelattice layers. The cation existing between the lattice layers isreferred to as an exchangeable cation and is exchangeable with variouscations. In particular, in the case where the cation between the latticelayers is Li+ or Na⁺, because of a small ionic radius, a bond betweenthe stratiform crystal lattices is week, and the inorganic stratiformcompound greatly swells upon contact with water. When share is appliedunder such condition, the stratiform crystal lattices are easily cleavedto form a stable sol in water. The bentnite and swellable synthetic micahave strongly such tendency and are useful in the invention.Particularly, the swellable synthetic mica is preferably used.

With respect to the shape of the inorganic stratiform compound used inthe invention, the thinner the thickness or the larger the plain size aslong as smoothness of coated surface and transmission of actinicradiation are not damaged, the better from the standpoint of control ofdiffusion. Therefore, an aspect ratio of the inorganic stratiformcompound is ordinarily 20 or more, preferably 100 or more, andparticularly preferably 200 or more. The aspect ratio is a ratio ofthickness to major axis of particle and can be determined, for example,from a projection drawing of particle by a microphotography. The largerthe aspect ratio, the greater the effect obtained.

As for the particle size of the inorganic stratiform compound used inthe invention, an average major axis is ordinarily from 0.3 to 20 μm,preferably from 0.5 to 10 μm, and particularly preferably from 1 to 5μm. An average thickness of the particle is ordinarily 0.1 μm or less,preferably 0.05 μm or less, and particularly preferably 0.01 μm or less.For example, in the swellable synthetic mica that is the representativecompound of the inorganic stratiform compounds, thickness isapproximately from 1 to 50 nm and plain size is approximately from 1 to20 μm.

When such an inorganic stratiform compound particle having a largeaspect ratio is incorporated into the protective layer, strength ofcoated layer increases and penetration of oxygen or moisture can beeffectively inhibited so that the protective layer can be prevented fromdeterioration due to deformation, and even when the lithographicprinting plate precursor is preserved for a long period of time under ahigh humidity condition, it is prevented from decrease in theimage-forming property thereof due to the change of humidity andexhibits excellent preservation stability.

The content of the inorganic stratiform compound in the protective layeris preferably from 5/1 to 1/00 in terms of weight ratio to the amount ofbinder used in the protective layer. When a plurality of inorganicstratiform compounds is used in combination, it is also preferred thatthe total amount of the inorganic stratiform compounds fulfills theabove-described weight ratio.

An example of common dispersing method for the inorganic stratiformcompound used in the protective layer is described below. Specifically,from 5 to 10 parts by weight of a swellable stratiform compound that isexemplified as a preferred inorganic stratiform compound is added to 100parts by weight of water to adapt the compound to water and to beswollen, followed by dispersing using a dispersing machine. Thedispersing machine used include, for example, a variety of millsconducting dispersion by directly applying mechanical power, ahigh-speed agitation type dispersing machine providing a large shearforce and a dispersion machine providing ultrasonic energy of highintensity. Specific examples thereof include a ball mill, a sand agrinder mill, a visco mill, a colloid mill, a homogenizer, a dissolver,a polytron, a homomixer, a homoblender, a keddy mill, a jet agitor, acapillary type emulsifying device, a liquid siren, an electromagneticstrain type ultrasonic generator and an emulsifying device having aPolman whistle. A dispersion containing from 5 to 10% by weight of theinorganic stratiform compound thus prepared is highly viscous or gelledand exhibits extremely good preservation stability. In the formation ofa coating solution for protective layer using the dispersion, it ispreferred that the dispersion is diluted with water, sufficientlystirred and then mixed with a binder solution.

To the coating solution for protective layer can be added knownadditives, for example, a surfactant for improving coating property or awater-soluble plasticizer for improving physical property of coatedlayer in addition to the inorganic stratiform compound. Examples of thewater-soluble plasticizer include propionamide, cyclohexanediol,glycerin or sorbitol. Also, a water-soluble (meth)acrylic polymer can beadded. Further, to the coating solution may be added known additives forincreasing adhesion to the photosensitive layer or for improvingpreservation stability of the coating solution.

The coating solution for protective layer thus-prepared is coated on thephotosensitive layer provided on the support and then dried to form aprotective layer. The coating solvent may be appropriately selected inview of the binder used, and when a water-soluble polymer is used,distilled water or purified water is preferably used as the solvent. Acoating method of the protective layer is not particularly limited, andknown methods, for example, methods described in U.S. Pat. No. 3,458,311and JP-B-55-49729 can be utilized. Specific examples of the coatingmethod for the protective layer include a blade coating method, an airknife coating method, a gravure coating method, a roll coating method, aspray coating method, a dip coating method and a bar coating method.

A coating amount of the protective layer is preferably in a range from0.05 to 10 g/m² in terms of the coating amount after drying. When theprotective layer contains the inorganic stratiform compound, it is morepreferably in a range from 0.1 to 0.5 g/m², and when the protectivelayer does not contain the inorganic stratiform compound, it is morepreferably in a range from 0.5 to 5 g/m².

[Support]

The support for use in the lithographic printing plate precursoraccording to the invention is not particularly restricted as long as itis a dimensionally stable plate-like hydrophilic support. The supportincludes, for example, paper, paper laminated with plastic (for example,polyethylene, polypropylene or polystyrene), a metal plate (for example,aluminum, zinc or copper plate), a plastic film (for example, cellulosediacetate, cellulose triacetate, cellulose propionate, cellulosebutyrate, cellulose acetatebutyrate, cellulose nitrate, polyethyleneterephthalate, polyethylene, polystyrene, polypropylene, polycarbonateor polyvinyl acetal film) and paper or a plastic film laminated ordeposited with the metal described above. Preferable examples of thesupport include a polyester film and an aluminum plate. Among them, thealuminum plate is preferred since it has good dimensional stability andis relatively inexpensive.

The aluminum plate includes a pure aluminum plate, an alloy platecomprising aluminum as a main component and containing a trace amount ofhetero elements and a thin film of aluminum or aluminum alloy laminatedwith plastic. The hetero element contained in the aluminum alloyincludes, for example, silicon, iron, manganese, copper, magnesium,chromium, zinc, bismuth, nickel and titanium. The content of the heteroelement in the aluminum alloy is preferably 10% by weight or less.Although a pure aluminum plate is preferred in the invention, sincecompletely pure aluminum is difficult to be produced in view of therefining technique, the aluminum plate may slightly contain the heteroelement. The composition is not specified for the aluminum plate andthose materials known and used conventionally can be appropriatelyutilized.

The thickness of the support is preferably from 0.1 to 0.6 mm, morepreferably from 0.15 to 0.4 mm, and still more preferably from 0.2 to0.3 mm.

Prior to the use of aluminum plate, a surface treatment, for example,roughening treatment or anodizing treatment is preferably performed. Thesurface treatment facilitates improvement in the hydrophilic propertyand ensures adhesion between the photosensitive layer and the support.In advance of the roughening treatment of the aluminum plate, adegreasing treatment, for example, with a surfactant, an organic solventor an aqueous alkaline solution is conducted for removing rolling oil onthe surface thereof, if desired.

The roughening treatment of the surface of the aluminum plate isconducted by various methods and includes, for example, mechanicalroughening treatment, electrochemical roughening treatment (rougheningtreatment of electrochemically dissolving the surface) and chemicalroughening treatment (roughening treatment of chemically dissolving thesurface selectively).

As the method of the mechanical roughening treatment, a known method,for example, a ball grinding method, a brush grinding method, a blastgrinding method or a buff grinding method can be used.

The electrochemical roughening treatment method includes, for example, amethod of conducting it by passing alternating current or direct currentin an electrolyte containing an acid, for example, hydrochloric acid ornitric acid. Also, a method of using a mixed acid described inJP-A-54-63902 can be used.

The aluminum plate after the roughening treatment is then subjected, ifdesired, to an alkali etching treatment using an aqueous solution, forexample, of potassium hydroxide or sodium hydroxide and furthersubjected to a neutralizing treatment, and then subjected to ananodizing treatment in order to enhance the abrasion resistance, ifdesired.

As the electrolyte used for the anodizing treatment of the aluminumplate, various electrolytes capable of forming porous oxide film can beused. Ordinarily, sulfuric acid, hydrochloric acid, oxalic acid, chromicacid or a mixed acid thereof is used. The concentration of theelectrolyte can be appropriately determined depending on the kind of theelectrolyte.

Since the conditions of the anodizing treatment are varied depending onthe electrolyte used, they cannot be defined generally. However, it isordinarily preferred that electrolyte concentration in the solution isfrom 1 to 80% by weight, liquid temperature is from 5 to 70° C., currentdensity is from 5 to 60 A/dm², voltage is from 1 to 100 V, andelectrolysis time is from 10 seconds to 5 minutes. The amount of theanodized film formed is preferably from 1.0 to 5.0 g/m² and morepreferably from 1.5 to 4.0 g/m². In the above-described range, goodprinting durability and favorable scratch resistance in the non-imagearea of lithographic printing plate can be achieved.

The aluminum plate subjected to the surface treatment and having theanodized film is used as it is as the support in the invention. However,in order to more improve adhesion to a layer provided thereon,hydrophilicity, resistance to stain, heat insulating property or thelike, other treatment, for example, a treatment for enlarging microporesor a sealing treatment of micropores of the anodized film described inJP-A-2001-253181 and JP-A-2001-322365, or a surface hydrophilizingtreatment by immersing in an aqueous solution containing a hydrophiliccompound, may be appropriately conducted. Needless to say, the enlargingtreatment and sealing treatment are not limited to those described inthe above-described patents and any conventionally known method may beemployed.

As the sealing treatment, as well as a sealing treatment with steam, asealing treatment with an aqueous solution containing an inorganicfluorine compound, for example, fluorozirconic acid alone or sodiumfluoride, a sealing treatment with steam having added thereto lithiumchloride or a sealing treatment with hot water may be employed.

Among them, the sealing treatment with an aqueous solution containing aninorganic fluorine compound, the sealing treatment with water vapor anda sealing treatment with hot water are preferred.

The hydrophilizing treatment includes an alkali metal silicate methoddescribed in U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and3,902,734. In the method, the support is subjected to an immersiontreatment or an electrolytic treatment in an aqueous solution, forexample, of sodium silicate. In addition, the hydrophilizing treatmentincludes, for example, a method of treating with potassiumfluorozirconate described in JP-B-36-22063 and a method of treating withpolyvinylphosphonic acid described in U.S. Pat. Nos. 3,276,868,4,153,461, and 4,689,272.

In the case of using a support having a surface of insufficienthydrophilicity, for example, a polyester film, in the invention, it isdesirable to coat a hydrophilic layer thereon to make the surfacesufficiently hydrophilic. Examples of the hydrophilic layer preferablyincludes a hydrophilic layer formed by coating a coating solutioncontaining a colloid of oxide or hydroxide of at least one elementselected from beryllium, magnesium, aluminum, silicon, titanium, boron,germanium, tin, zirconium, iron, vanadium, antimony and a transitionmetal described in JP-A-2001-199175, a hydrophilic layer containing anorganic hydrophilic matrix obtained by crosslinking orpseudo-crosslinking of an organic hydrophilic polymer described inJP-A-2002-79772, a hydrophilic layer containing an inorganic hydrophilicmatrix obtained by sol-gel conversion comprising hydrolysis andcondensation reaction of polyalkoxysilane and titanate, zirconate oraluminate, and a hydrophilic layer comprising an inorganic thin layerhaving a surface containing metal oxide. Among them, the hydrophiliclayer formed by coating a coating solution containing a colloid of oxideor hydroxide of silicon is preferred.

Further, in the case of using, for example, a polyester film as thesupport in the invention, it is preferred to provide an antistatic layeron the hydrophilic layer side, opposite side to the hydrophilic layer orboth sides. When the antistatic layer is provided between the supportand the hydrophilic layer, it also contributes to improve the adhesionof the hydrophilic layer to the support. As the antistatic layer, apolymer layer having fine particles of metal oxide or a matting agentdispersed therein described in JP-A-2002-79772 can be used.

The support preferably has a center line average roughness of 0.10 to1.2 μm. In the above-described range, good adhesion to thephotosensitive layer, good printing durability, and good stainresistance can be achieved.

The color density of the support is preferably from 0.15 to 0.65 interms of the reflection density value. In the above-described range,good image-forming property by preventing halation at the image exposureand good aptitude for plate inspection after development can beachieved.

(Undercoat Layer)

In the lithographic printing plate precursor for use in the lithographicprinting method according to the invention, an undercoat layer can beprovided between the photosensitive layer and the support, if desired.It is advantageous that in the case of infrared laser exposure, sincethe undercoat layer acts as a heat insulating layer, heat generated uponthe exposure does not diffuse into the support and is efficientlyutilized so that increase in sensitivity can be achieved. Further, theundercoat layer makes removal of the photosensitive layer from thesupport in the unexposed area easy so that the on-machine developmentproperty can be improved.

As a compound for the undercoat layer, specifically, for example, asilane coupling agent having an addition-polymerizable ethylenic doublebond reactive group described in JP-A-10-282679 and a phosphoruscompound having an ethylenic double bond reactive group described inJP-A-2-304441 are preferably exemplified.

As the most preferable compound for undercoat layer, a polymer resinobtained by copolymerization of a monomer having an adsorbing group, amonomer having a hydrophilic group and a monomer having a crosslinkablegroup is exemplified.

The essential component in the polymer undercoat layer is an adsorbinggroup to the hydrophilic surface of the support. Whether theadsorptivity to the hydrophilic surface of the support is present or notcan be judged, for example, by the following method.

Specifically, a test compound is dissolved in a solvent in which thetest compound is easily soluble to prepare a coating solution, and thecoating solution is coated and dried on a support so as to have thecoating amount after drying of 30 mg/m². After thoroughly washing thesupport coated with the test compound using the solvent in which thetest compound is easily soluble, the residual amount of the testcompound that has not been removed by the washing is measured tocalculate the adsorption amount to the support. For measurement of theresidual amount, the amount of the residual test compound may bedirectly determined, or it may be calculated from the amount of the testcompound dissolved in the washing solution. The determination for thecompound can be performed, for example, by fluorescent X-raymeasurement, reflection spectral absorbance measurement or liquidchromatography measurement. The compound having the adsorptivity tosupport means a compound that remains by 1 mg/m² or more even afterconducting the washing treatment described above.

The adsorbing group to the hydrophilic surface of the support is afunctional group capable of forming a chemical bond (for example, anionic bond, a hydrogen bond, a coordinate bond or a bond withintermolecular force) with a substance (for example, metal or metaloxide) or a functional group (for example, a hydroxy group) present onthe surface of the support. The adsorbing group is preferably an acidgroup or a cationic group.

The acid group preferably has an acid dissociation constant (pKa) of 7or less. Examples of the acid group include a phenolic hydroxy group, acarboxyl group, —SO₃H, —OSO₃H, —PO₃H₂, —OPO₃H₂, —CONHSO₂—, —SO₂NHSO₂—and —COCH₂COCH₃. Among them, —OPO₃H₂ and —PO₃H₂ are particularlypreferred. The acid group may be the form of a metal salt.

The cationic group is preferably an onium group. Examples of the oniumgroup include an ammonium group, a phosphonium group, an arsonium group,a stibonium group, an oxonium group, a sulfonium group, a selenoniumgroup, a stannonium group and iodonium group. Among them, the ammoniumgroup, phosphonium group and sulfonium group are preferred, the ammoniumgroup and phosphonium group are more preferred, and the ammonium groupis most preferred.

Particularly preferable examples of the monomer having the adsorbinggroup include compounds represented by the following formula (VII) or(VIII):

In formula (VII) or (VIII), R¹, R² and R³ each independently representsa hydrogen atom, halogen atom or an alkyl group having from 1 to 6carbon atoms. R¹ and R² and R³ each independently represents preferablya hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, morepreferably a hydrogen atom or an alkyl group having from 1 to 3 carbonatoms, and most preferably a hydrogen atom or a methyl group. It isparticularly preferred that R² and R³ each represents a hydrogen atom.

In the formula (VII), X represents an oxygen atom (—O—) or imino group(—NH—). Preferably, X represents an oxygen atom. In the formula (VII) or(VIII), L represents a divalent connecting group. It is preferred that Lrepresents a divalent aliphatic group (for example, an alkylene group, asubstituted alkylene group, an alkenylene group, a substitutedalkenylene group, an alkinylene group or a substituted alkinylenegroup), a divalent aromatic group (for example, an arylene group or asubstituted arylene group), a divalent heterocyclic group or acombination of each of the groups described above with an oxygen atom(—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted iminogroup (—NR—, wherein R represents an aliphatic group, an aromatic groupor a heterocyclic group) or a carbonyl group (—CO—).

The aliphatic group may form a cyclic structure or a branched structure.The number of carbon atoms of the aliphatic group is preferably from 1to 20, more preferably from 1 to 15, and most preferably from 1 to 10.It is preferred that the aliphatic group is a saturated aliphatic grouprather than an unsaturated aliphatic group. The aliphatic group may havea substituent. Examples of the substituent include a halogen atom, ahydroxy group, an aromatic group and a heterocyclic group.

The number of carbon atoms of the aromatic group is preferably from 6 to20, more preferably from 6 to 15, and most preferably from 6 to 10. Thearomatic group may have a substituent. Examples of the substituentinclude a halogen atom, a hydroxy group, an aliphatic group, an aromaticgroup and a heterocyclic group.

It is preferred that the heterocyclic group has a 5-membered or6-membered ring as the hetero ring. Other heterocyclic ring, analiphatic ring or an aromatic ring may be condensed to the heterocyclicring. The heterocyclic group may have a substituent. Examples of thesubstituent include a halogen atom, a hydroxy group, an oxo group (═O),a thioxo group (═S), an imino group (═NH), a substituted imino group(═N—R, where R represents an aliphatic group, an aromatic group or aheterocyclic group), an aliphatic group, an aromatic group and aheterocyclic group.

It is preferred that L represents a divalent connecting group containinga plurality of polyoxyalkylene structures. It is more preferred that thepolyoxyalkylene structure is a polyoxyethylene structure. Specifically,it is preferred that L contains —(OCH₂CH₂)_(n)— (n is an integer of 2 ormore).

In the formula (VII) or (VIII), Z represents a functional groupadsorbing to the hydrophilic surface of the support. In the formula(VIII), Y represents a carbon atom or a nitrogen atom. In the case whereY is a nitrogen atom and L is connected to Y to form a quaternarypyridinium group, Z is not mandatory, because the quaternary pyridiniumgroup itself exhibits the adsorptivity. The adsorptive functional groupis the same as that described above.

Representative examples of the monomer represented by formula (VII) or(VIII) are set forth below.

The hydrophilic group of the polymer resin for undercoat layer which canbe used in the invention includes, for example, a hydroxy group, acarboxyl group, a carboxylate group, a hydroxyethyl group, apolyoxyethyl group, a hydroxypropyl group, a polyoxypropyl group, anamino group, an aminoethyl group, an aminopropyl group, an ammoniumgroup, an amido group, a carboxymethyl group, a sulfonic acid group anda phosphoric acid group. A monomer containing such a hydrophilic groupand a polymerizable group is employed as a copolymerization component ofthe polymer resin for undercoat layer.

The polymer resin for undercoat layer which can be used in the inventionpreferably includes a crosslinkable group. By the crosslinkable group,increase in adhesion to the image area can be achieved. In order toimpart the crosslinkable property to the polymer resin for the undercoatlayer, introduction of a crosslinkable functional group, for example, anethylenically unsaturated bond into the side chain of the polymer resin,or introduction by formation of a salt structure between a polarsubstituent of the polymer resin and a compound containing a substituenthaving a counter charge to the polar substituent of the polymer resinand an ethylenically unsaturated bond is carried out.

Examples of the polymer having an ethylenically unsaturated bond in theside chain thereof include a polymer of an ester or amide of acrylicacid or methacrylic acid, which is a polymer wherein the ester or amideresidue (R in —COOR or —CONHR) has an ethylenically unsaturated bond.

Examples of the residue (R described above) having an ethylenicallyunsaturated bond include —(CH₂)_(n)CR₁═CR₂R₃, —(CH₂O)_(n)CH₂CR₁═CR₂R₃,—(CH₂CH₂O)_(n)CH₂CR₁═CR₂R₃, —(CH₂)_(n)NH—CO—O—CH₂CR₁═CCR₂R₃,—(CH₂)_(n)—O—CO—CR₁═CCR₂R₃ and —(CH₂CH₂O)₂—X (wherein R₁ to R₃ eachindependently represents a hydrogen atom, a halogen atom or an alkylgroup having from 1 to 20 carbon atoms, an aryl group, alkoxy group oraryloxy group, or R₁ and R₂ or R₁ and R₃ may be combined with each otherto form a ring. n represents an integer of 1 to 10. X represents adicyclopentadienyl residue).

Specific examples of the ester residue include —CH₂CH═CH₂ (described inJP-B-7-21633) —CH₂CH₂O—CH₂CH═CH₂, —CH₂C(CH₃)═CH₂, —CH₂CH═CH—C₆H₅,—CH₂CH₂OCOCH═CH—C₆H₅, —CH₂CH₂—NHCOO—CH₂CH═CH₂ and —CH₂CH₂O—X (wherein Xrepresents a dicyclopentadienyl residue).

Specific examples of the amide residue include —CH₂CH═CH₂, —CH₂CH₂O—Y(wherein Y represents a cyclohexene residue) and —CH₂CH₂—OCO—CH═CH₂.

As the monomer having a crosslinkable group for the polymer resin forthe undercoat layer, an ester or amide of acrylic acid or methacrylicacid having the above-described crosslinkable group is preferable.

A content of the crosslinking group in the polymer resin for undercoatlayer (content of the radical polymerizable unsaturated double bonddetermined by iodine titration) is preferably from 0.1 to 10.0 mmol,more preferably from 1.0 to 7.0 mmol, and most preferably from 2.0 to5.5 mmol, based on 1 g of the polymer resin. In the above-describedrange, preferable compatibility between the sensitivity and stainresistance and good preservation stability can be achieved.

A weight average molecular weight of the polymer resin for undercoatlayer is preferably 5,000 or more, more preferably from 10,000 to300,000. A number average molecular weight of the polymer resin forundercoat layer is preferably 1,000 or more, more preferably from 2,000to 250,000. The polydispersity (weight average molecular weight/numberaverage molecular weight) thereof is preferably from 1.1 to 10.

The polymer resin for undercoat layer may be any of a random polymer, ablock polymer and a graft polymer, and it is preferably a randompolymer.

As the polymer resin for undercoat layer, known resins having ahydrophilic group can also be used. Specific examples of the resininclude gum arabic, casein, gelatin, a starch derivative, carboxy methylcellulose and a sodium salt thereof, cellulose acetate, sodium alginate,vinyl acetate-maleic acid copolymer, styrene-maleic acid copolymer,polyacrylic acid and a salt thereof, polymethacrylic acid and a saltthereof, a homopolymer or copolymer of hydroxyethyl methacrylate, ahomopolymer or copolymer of hydroxyethyl acrylate, a homopolymer orcopolymer of hydroxypropyl methacrylate, a homopolymer or copolymer ofhydroxypropyl acrylate, a homopolymer or copolymer of hydroxybutylmethacrylate, a homopolymer or copolymer of hydroxybutyl acrylate, apolyethylene glycol, a hydroxypropylene polymer, a polyvinyl alcohol, ahydrolyzed polyvinyl acetate having a hydrolysis degree of 60% by moleor more, preferably 80% by mole or more, a polyvinyl formal, a polyvinylbutyral, a polyvinyl pyrrolidone, a homopolymer or copolymer ofacrylamide, a homopolymer or polymer of methacrylamide, a homopolymer orcopolymer of N-methylolacrylamide, a polyvinyl pyrrolidone, analcohol-soluble nylon, a polyether of 2,2-bis-(4-hydroxyphenyl)propaneand epichlorohydrin.

The polymer resins for undercoat layer may be used individually or as amixture of two or more thereof.

A coating amount (solid content) of the undercoat layer is preferablyfrom 0.1 to 100 mg/m² , and more preferably from 1 to 30 mg/m².

(Backcoat Layer)

After applying the surface treatment to the support or forming theundercoat layer on the support, a backcoat layer can be provided on theback surface of the support, if desired.

The backcoat layer preferably includes, for example, a coating layercomprising an organic polymer compound described in JP-A-5-45885, and acoating layer comprising a metal oxide obtained by hydrolysis andpolycondensation of an organic metal compound or an inorganic metalcompound described in JP-A-6-35174. Among them, use of an alkoxycompound of silicon, for example, Si(OCH₃)₄, Si(OC₂H₅)₄, Si(OC₃H₇)₄ orSi(OC₄H₉)₄ is preferred since the starting material is inexpensive andeasily available.

[Plate-Making Method]

The lithographic printing plate precursor according to the invention isexposed imagewise by a light source of 350 to 450 nm, and then rubbed asurface of the exposed lithographic printing plate precursor with arubbing member in the presence of a developer having pH of 2 to 10 in anautomatic processor to remove the protective layer and the unexposedarea of the photosensitive layer all at once, whereby an image can beformed on the surface of aluminum plate support.

Specifically, after removing the protective layer and the unexposed areaof the photosensitive layer all at once, the resulting printing plate isimmediately mounted on a printing machine to conduct printing.

The processing by the automatic processor in such a manner isadvantageous in view of being free from the measures against developmentscum resulting from the protective layer and photosensitive layerencountered in case of on-machine development.

The developer for use in the invention is an aqueous solution having pHof 2 to 10. For instance, the developer is preferably water alone or anaqueous solution containing water as a main component (containing 60% byweight or more of water). Particularly, an aqueous solution having thesame composition as conventionally known dampening water, an aqueoussolution containing a surfactant (for example, an anionic, nonionic orcationic surfactant) and an aqueous solution containing a water-solublepolymer compound are preferable. An aqueous solution containing both asurfactant and a water-soluble polymer compound is especiallypreferable. The pH of the developer is preferably from 3 to 8, and morepreferably from 4 to 7.

The concentration of the surfactant in the developer is ordinarily 1% byweight or more, preferably 2% by weight or more, and more preferablyfrom 5 to 20% by weight or more.

The anionic surfactant for use in the developer according to theinvention includes, for example, fatty acid salts, abietic acid salts,hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,dialkylsulfosuccinic acid salts, straight-chain alkylbenzenesulfonicacid salts, branched alkylbenzenesulfonic acid salts,alkylnaphthalenesulfonic acid salts, alkylphenoxypolyoxy ethylenepropylsulfonic acid salts, polyoxyethylene alkylsulfophenyl ether salts,N-methyl-N-oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamidedisodium salts, petroleum sulfonic acid salts, sulfated castor oil,sulfated beef tallow oil, sulfate ester slats of fatty acid alkyl ester,alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate estersalts, fatty acid monoglyceride sulfate ester salts, polyoxyethylenealkyl phenyl ether sulfate ester salts, polyoxyethylene styryl phenylether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylenealkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl etherphosphate ester salts, partially saponified products of styrene-maleicanhydride copolymer, partially saponified products of olefin-maleicanhydride copolymer and naphthalene sulfonate formalin condensates. Ofthe compounds, dialkylsulfosuccinic acid salts, alkyl sulfate estersalts and alkylnaphthalenesulfonic acid salts are particularlypreferably used.

The cationic surfactant for use in the developer according to theinvention is not particularly limited and conventionally known cationicsurfactants can be used. Examples of the cationic surfactant includealkylamine salts, quaternary ammonium salts, polyoxyethylene alkyl aminesalts and polyethylene polyamine derivatives.

The nonionic surfactant for use in the developer according to theinvention includes, for example, polyethylene glycol type higher alcoholethylene oxide addacts, alkylphenol ethylene oxide addacts, fatty acidethylene oxide addacts, polyhydric alcohol fatty acid ester ethyleneoxide addacts, higher alkylamine ethylene oxide addacts, fatty acidamide ethylene oxide addacts, ethylene oxide addacts of fat,polypropylene glycol ethylene oxide addacts, dimethylsiloxane-ethyleneoxide block copolymers, dimethylsiloxane-(propylene oxide-ethyleneoxide) block copolymers, fatty acid esters of polyhydric alcohol typeglycerol, fatty acid esters of pentaerythritol, fatty acid esters ofsorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers ofpolyhydric alcohols and fatty acid amides of alkanolamines.

The nonionic surfactants may be used individually or as a mixture of twoor more thereof. In the invention, ethylene oxide addacts of sorbitoland/or sorbitan fatty acid esters, polypropylene glycol ethylene oxideaddacts, dimethylsiloxane-ethylene oxide block copolymers,dimethylsiloxane-(propylene oxide-ethylene oxide) block copolymers andfatty acid esters of polyhydric alcohols are more preferable.

Further, from the standpoint of stable solubility in water or opacity,with respect to the nonionic surfactant used in the developer accordingto the invention, the HLB (hydrophile-lipophile balance) value thereofis preferably 6 or more, and more preferably 8 or more. Moreover, anamount of the nonionic surfactant contained in the developer ispreferably from 0.01 to 10% by weight, and more preferably from 0.01 to5% by weight.

Furthermore, an oxyethylene adduct of acetylene glycol type or acetylenealcohol type or a surfactant, for example, a fluorine-based surfactantor a silicon-based surfactant can also be used.

Of the surfactants used in the developer according to the invention, thenonionic surfactant is particularly preferred in view of foam depressingproperty.

Of the surfactants for use in the developer according to the invention,as the anionic surfactants, compounds represented by any one of formulae(III) to (VI) shown below are particularly preferable and as thenonionic or cationic surfactants containing a nitrogen atom, compoundsrepresented by any one of formulae (VII) to (IX) shown below areparticularly preferable.

The surfactants represented by any one of formulae (III) to (XI) shownbelow can be synthesized according to known methods. The molecularweight of the surfactant is ordinarily 2,000 or less, preferably from100 to 1,500.

In formulae, R₁ to R₁₀ each represents a hydrogen atom or an alkylgroup; 1 represents an integer of 1 to 3; X₁ and X₂ each represents asulfonate, a sulfuric monoester salt, a carboxylate or a phosphate; andprovided that a total number of carbon atoms included in R₁ to R₅ or R₆to R₁₀ is 3 or more.

In the compound represented by formula (III), when the total number ofcarbon atoms included in R₁ to R₅ is 3 or more, the effect can berecognized. However, as the total number of carbon atoms included in R₁to R₅ increases, the hydrophobic portion becomes large and dissolutionof the compound in an aqueous developer becomes difficult. In such acase, the surfactant can not be dissolved in a proper mixing range evenwhen a dissolution auxiliary agent for assisting the dissolution, forexample, an organic solvent is mixed with water. Ordinarily, the totalnumber of carbon atoms included in R₁ to R₅ is 24 or less. The totalnumber of carbon atoms included in R₁ to R₅ is preferably from 3 to 20.When R₁ to R₅ represent one or more alkyl groups, each of the alkylgroups may be a straight-chain or branched structure.

The total number of carbon atoms included in R₁ to R₅ of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, the total number of carbon atoms included in R₁ to R₅ may berelatively small. On the other hand, when a binder having lowhydrophilicity is used, it is necessary that the total number of carbonatoms included in R₁ to R₅ is large.

In the above-described compound, X₁ represents a sulfonate, a sulfuricmonoester salt, a carboxylate or a phosphate. Among them, the sulfonateand carboxylate have the large effect. In the salts, an alkali metalsalt is preferable, since it has excellent solubility in an aqueoussolvent. Among them, a sodium salt or a potassium salt is particularlypreferable.

The compound will be described more specifically below.

Specific examples of the compound wherein the alkyl groups representedby R₁ to R₅ do not contain an oxygen atom are set forth below.

Specific examples of the compound represented by formula (III) whereinat least one of R₁ to R₅ represents an alkyl group containing an oxygenatom, that is, —C_(m)H_(2m)OC_(n−m)H_(2(n−m)+1) (n≧2, n≧m≧0) are setforth below.

The substituents other than the —C_(m)H_(2m)OC_(n−m)H_(2(n−m)+1) arehydrogen atoms or alkyl groups, and the total number of carbon atomsincluded in R₁ to R₅ is 3 to 24. These compounds are easily soluble inthe aqueous solvent by the introduction of oxygen atom and they arepreferably used in the developer in many cases.

In the compound represented by formula (IV), when the total number ofcarbon atoms included in R₆ to R₁₀ is 3 or more, the effect can berecognized. However, as the total number of carbon atoms included in R₆to R₁₀ increases, the hydrophobic portion becomes large and dissolutionof the compound in an aqueous developer becomes difficult. In such acase, the surfactant can not be dissolved in a proper mixing range evenwhen a dissolution auxiliary agent for assisting the dissolution, forexample, an organic solvent is mixed with water. Ordinarily, the totalnumber of carbon atoms included in R₆ to R₁₀ is 24 or less. The totalnumber of carbon atoms included in R₆ to R₁₀ is preferably from 3 to 20.When R₆ to R₁₀ represents one or more alkyl groups, each of the alkylgroups may be a straight-chain or branched structure.

The total number of carbon atoms included in R₆ to R₁₀ of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, the total number of carbon atoms included in R₆ to R₁₀ may berelatively small. On the other hand, when a binder having lowhydrophilicity is used, it is necessary that the total number of carbonatoms included in R₆ to R₁₀ is large.

In the above-described compound, X₂ represents a sulfonate, a sulfuricmonoester salt, a carboxylate or a phosphate. Among them, the sulfonateand carboxylate have the large effect. In the salts, an alkali metalsalt is preferable, since it has excellent solubility in an aqueoussolvent. Among them, a sodium salt or a potassium salt is particularlypreferable.

The compound will be described more specifically below.

Specific examples of the compound wherein the alkyl groups representedby R₆ to R₁₀ do not contain an oxygen atom are set forth below.

Specific examples of the compound wherein at least one of R₆ to R₁₀represents an alkyl group containing an oxygen atom, that is,—C_(m)H_(2m)OC_(n−m)H_(2(n−m)+1) (n≧2, n≧m≧0) are set forth below.

The substituents other than the —C_(m)H_(2m)OC_(n−m)H_(2(n−m)+1) arehydrogen atoms or alkyl groups, and the total number of carbon atomsincluded in R₆ to R₁₀ is 3 to 24. These compounds are easily soluble inthe aqueous solvent by the introduction of oxygen atom and they arepreferably used in the developer in many cases.

In the formulae, R₁ to R₁₀ each represents a hydrogen atom or an alkylgroup; I represents an integer of 1 to 3; X₁ and X₂ each represents asulfonate, a sulfuric monoester salt, a carboxylate or a phosphate; Y₁and Y₂ each represents —C_(n)H_(2n)—, —C_(n−m)H_(2(n−m))OC_(m)H_(2m)—,—O—(CH₂CH₂O)_(n)—, —O—(CH₂CH₂CH₂O)_(n)— or —CO—NH— wherein n≧1 andn≧m≧0; and provided that a total number of carbon atoms included in R₁to R₅ and Y₁ or R₆ to R₁₀ and Y₂ is 3 or more.

In the compound represented by formula (V), when the total number ofcarbon atoms included in R₁ to R₅ and Y₁ is 3 or more, the effect can berecognized. However, as the total number of carbon atoms increases, thehydrophobic portion becomes large and dissolution of the compound in anaqueous developer becomes difficult. In such a case, the surfactant cannot be dissolved in a proper mixing range even when a dissolutionauxiliary agent for assisting the dissolution, for example, an organicsolvent is mixed with water. Ordinarily, the total number of carbonatoms is 25 or less. The total number of carbon atoms is preferably from4 to 20. The alkyl group described above may be a straight-chain orbranched structure.

The total number of carbon atoms included in R₁ to R₅ and Y₁ of thecompound (surfactant) is influenced by a material, especially, a binder,used in the photosensitive layer. When a binder having highhydrophilicity is used, the total number of carbon atoms included in R₁to R₅ and Y₁ may be relatively small. On the other hand, when a binderhaving low hydrophilicity is used, it is necessary that the total numberof carbon atoms is large.

In the above-described compound, X₁ represents a sulfonate, a sulfuricmonoester salt, a carboxylate or a phosphate. Among them, the sulfonateand carboxylate have the large effect. In the salts, an alkali metalsalt is preferable, since it has excellent solubility in an aqueoussolvent. Among them, a sodium salt or a potassium salt is particularlypreferable.

The compound will be described more specifically below.

Specific examples of the compound wherein Y₁ represents a group notcontaining an oxygen atom are set forth below.

Specific examples of the compound wherein Y₁ represents a groupcontaining an oxygen atom, that is, —C_(n−m)H_(2(n−m))OC_(m)H_(2m)—(n≧1, n≧m≧0) are set forth below.

The substituents (R₁ to R₅) other than the—C_(n−m)H_(2(n−m))OC_(m)H_(2m)— are hydrogen atoms or alkyl groups, andthe total number of carbon atoms is 3 to 25. These compounds are easilysoluble in the aqueous solvent by the introduction of oxygen atom andthey are preferably used in the developer in many cases.

In the compound represented by formula (VI), when the total number ofcarbon atoms included in R₆ to R₁₀ and Y₂ is 3 or more, the effect canbe recognized. However, as the total number of carbon atoms increases,the hydrophobic portion becomes large and dissolution of the compound inan aqueous developer becomes difficult. In such a case, the surfactantcan not be dissolved in a proper mixing range even when a dissolutionauxiliary agent for assisting the dissolution, for example, an organicsolvent is mixed with water. Ordinarily, the total number of carbonatoms is 25 or less. The total number of carbon atoms is preferably from3 to 20. The alkyl group described above may be a straight-chain orbranched structure.

The total number of carbon atoms included in R₆ to R₁₀ and Y₂ of thecompound (surfactant) is influenced by a material, especially, a binder,used in the photosensitive layer. When a binder having highhydrophilicity is used, the total number of carbon atoms included in R₆to R₁₀ and Y₂ may be relatively small. On the other hand, when a binderhaving low hydrophilicity is used, it is necessary that the total numberof carbon atoms is large.

In the above-described compound, X₂ represents a sulfonate, a sulfuricmonoester salt, a carboxylate or a phosphate. Among them, the sulfonateand carboxylate have the large effect. In the salts, an alkali metalsalt is preferable, since it has excellent solubility in an aqueoussolvent. Among them, a sodium salt or a potassium salt is particularlypreferable.

The compound will be described more specifically below.

Specific examples of the compound wherein Y₂ represents a group notcontaining an oxygen atom are set forth below.

Specific examples of the compound wherein Y₂ represents a groupcontaining an oxygen atom, that is, —C_(n−m)H_(2(n−m))OC_(m)H_(2m)—(n≧1, n≧m≧0) are set forth below.

The substituents (R₆ to R₁₀) other than the—C_(n−m)H_(2(n−m))OC_(m)H_(2m)— are hydrogen atoms or alkyl groups, andthe total number of carbon atoms is 3 to 25. These compounds are easilysoluble in the aqueous solvent by the introduction of oxygen atom andthey are preferably used in the developer in many cases.

In formula (VII), R_(a) represents a hydrogen atom or an alkyl group;and A and B each represents a group containing an ethylene oxide group,a carboxylic acid group or a carboxylate.

In formula (VIII), R_(b) and R_(c) each represents a hydrogen atom or analkyl group; C represents an alkyl group or a group containing anethylene oxide group; and D represents a group containing a carboxylicacid anion.

In formula (IX), R_(d), R_(e), R_(f) and R_(g) each represents ahydrogen atom or an alkyl group; and Z⁻ represents a counter anion.

The alkyl group represented by any one of R_(a) and R_(g) may have asubstituent.

The compounds (hereinafter, also referred to as surfactant) representedby formulae (VII), (VIII) and (IX) described above are not particularlyrestricted. Representative compounds are described below.

In the formula, R11 to R13, R15, R16, R18, R21 and R24 to R27 eachrepresents a hydrogen atom or an alkyl group, and R14, R17, R19, R20,R22 and R23 each represents an alkylene group or a single bond.

In the compound represented by formula (10), R11 to R13 each representsa hydrogen atom or an alkyl group, and R14 represents an alkylene group.However, the N atom may be directly connected with the carboxyl groupand in this case, R14 represents a single bond.

In the compound represented by formula (10), as the total number ofcarbon atoms increases, the hydrophobic portion becomes large anddissolution of the compound in an aqueous developer becomes difficult.In such a case, the dissolution is improved by mixing a dissolutionauxiliary agent for assisting the dissolution, for example, an organicsolvent or an alcohol. However, when the total number of carbon atomsexcessively increases, the surfactant can not be dissolved in a propermixing range. The total number of carbon atoms included in R11 to R14 ispreferably from 10 to 40, more preferably from 12 to 30.

When R11 to R13 each represents an alkyl group, the alkyl group may be astraight-chain or branched structure.

The total number of carbon atoms included in R11 to R14 of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, it tends to be preferable that the total number of carbon atomsincluded in R11 to R14 is relatively small. On the other hand, when abinder having low hydrophilicity is used, it is preferable that thetotal number of carbon atoms included in R11 to R14 is large.

Specific examples of the representative compound are set forth below.

In the compound represented by formula (11), R15 to R16 each representsa hydrogen atom or an alkyl group, and R17 represents an alkylene group.However, the N atom may be directly connected with the carboxyl groupand in this case, R17 represents a single bond.

Similar to the compound represented by formula (10), in the compoundrepresented by formula (11), as the total number of carbon atomsincreases, the hydrophobic portion becomes large and dissolution of thecompound in an aqueous developer becomes difficult. In such a case, thedissolution is improved by mixing a dissolution auxiliary agent forassisting the dissolution, for example, an organic solvent or analcohol. However, when the total number of carbon atoms excessivelyincreases, the surfactant can not be dissolved in a proper mixing range.The total number of carbon atoms included in R15 to R17 is preferablyfrom 10 to 30, more preferably from 12 to 25.

When R15 to R17 each represents an alkyl group, the alkyl group may be astraight-chain or branched structure.

The total number of carbon atoms included in R15 to R17 of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, it tends to be preferable that the total number of carbon atomsincluded in R15 to R17 is relatively small. On the other hand, when abinder having low hydrophilicity is used, it is preferable that thetotal number of carbon atoms included in R15 to R17 is large.

In the compound described above, as X⁺, a divalent metal ion, forexample, a calcium ion or a magnesium ion, an ammonium ion or a hydrogenion is used in addition to a monovalent metal ion, for example, apotassium ion or a sodium ion. Among them, a sodium ion or a potassiumion is preferably used.

Specific examples of the representative compound are set forth below.

In the compound represented by formula (12), R18 represents a hydrogenatom or an alkyl group, and R19 and R20 each represents an alkylenegroup. However, the N atom may be directly connected with the carboxylgroups and in this case, R19 and R20 each represents a single bond.

Similar to the compound represented by formula (10) or (11), in thecompound represented by formula (12), as the total number of carbonatoms increases, the hydrophobic portion becomes large and dissolutionof the compound in an aqueous developer becomes difficult. In such acase, the dissolution is improved by mixing a dissolution auxiliaryagent for assisting the dissolution, for example, an organic solvent oran alcohol. However, when the total number of carbon atoms excessivelyincreases, the surfactant can not be dissolved in a proper mixing range.The total number of carbon atoms included in R18 to R20 is preferablyfrom 10 to 30, more preferably from 12 to 28.

When R18 represents an alkyl group, the alkyl group may be astraight-chain or branched structure.

The total number of carbon atoms included in R18 to R20 of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, it tends to be preferable that the total number of carbon atomsincluded in R18 to R20 is relatively small. On the other hand, when abinder having low hydrophilicity is used, it is preferable that thetotal number of carbon atoms included in R18 to R20 is large.

In the compound described above, as X⁺ or Y⁺, a divalent metal ion, forexample, a calcium ion or a magnesium ion, an ammonium ion or a hydrogenion is used in addition to a monovalent metal ion, for example, apotassium ion or a sodium ion. Among them, a sodium ion or a potassiumion is preferably used.

Specific examples of the representative compound are set forth below.

In the compound represented by formula (13), R21 represents a hydrogenatom or an alkyl group, and R22 and R23 each represents an alkylenegroup. However, the N atom may be directly connected with the ethyleneoxide groups and in this case, R22 and R23 each represents a singlebond.

In the compound represented by formula (13) also, as the total number ofcarbon atoms increases, the hydrophobic portion becomes large anddissolution of the compound in an aqueous developer becomes difficult.In such a case, the dissolution is improved by mixing a dissolutionauxiliary agent for assisting the dissolution, for example, an organicsolvent or an alcohol. However, when the total number of carbon atomsexcessively increases, the surfactant can not be dissolved in a propermixing range. The total number of carbon atoms included in R21 to R23 ispreferably from 8 to 50, more preferably from 12 to 40.

When R21 represents an alkyl group, the alkyl group may be astraight-chain or branched structure.

The total number of carbon atoms included in R21 to R23 of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, it tends to be preferable that the total number of carbon atomsincluded in R21 to R23 is relatively small. On the other hand, when abinder having low hydrophilicity is used, it is preferable that thetotal number of carbon atoms included in R21 to R23 is large.

With respect to m and n each representing a number of the ethyleneoxide, as the number increases, the hydrophilicity increases and thestability thereof in water is improved. m and n may be the same ordifferent. m is ordinarily from 1 to 20 and n is ordinarily from 1 to20.

Specific examples of the representative compound are set forth below.

In the compound represented by formula (14), R24 to R27 each representsa hydrogen atom or an alkyl group.

In the compound represented by formula (14) also, as the total number ofcarbon atoms increases, the hydrophobic portion becomes large anddissolution of the compound in an aqueous developer becomes difficult.In such a case, the dissolution is improved by mixing a dissolutionauxiliary agent for assisting the dissolution, for example, an organicsolvent or an alcohol. However, when the total number of carbon atomsexcessively increases, the surfactant can not be dissolved in a propermixing range. The total number of carbon atoms included in R24 to R27 ispreferably from 10 to 30, more preferably from 12 to 28.

When R24 to R27 each represents an alkyl group, the alkyl group may be astraight-chain or branched structure.

The total number of carbon atoms included in R24 to R27 of the compound(surfactant) is influenced by a material, especially, a binder, used inthe photosensitive layer. When a binder having high hydrophilicity isused, it tends to be preferable that the total number of carbon atomsincluded in R24 to R27 is relatively small. On the other hand, when abinder having low hydrophilicity is used, it is preferable that thetotal number of carbon atoms included in R24 to R27 is large.

Z⁻ represents a counter anion. The counter anion is not restricted but,for example, Cl⁻, Br⁻ or I⁻ is used in many cases.

Specific examples of the representative compound are set forth below.

The water-soluble polymer compound for use in the developer according tothe invention includes, for example, soybean polysaccharide, modifiedstarch, gum arabic, dextrin, a cellulose derivative (for example,carboxymethyl cellulose, carboxyethyl cellulose or methyl cellulose) ora modified product thereof, pllulan, polyvinyl alcohol or a derivativethereof, polyvinyl pyrrolidone, polyacrylamide, an acrylamide copolymer,a vinyl methyl ether/maleic anhydride copolymer, a vinyl acetate/maleicanhydride copolymer and a styrene/maleic anhydride copolymer.

As the soybean polysaccharide, those known can be used. For example, asa commercial product, Soyafive (trade name, produced by Fuji Oil Co.,Ltd.) is available and various grade products can be used. The soybeanpolysaccharide preferably used has viscosity in a range from 10 to 100mPa/sec in a 10% by weight aqueous solution thereof.

As the modified starch, known modified starch can be used. The modifiedstarch can be prepared, for example, by a method wherein starch, forexample, of corn, potato, tapioca, rice or wheat is decomposed, forexample, with an acid or an enzyme to an extent that the number ofglucose residue per molecule is from 5 to 30 and then oxypropylene isadded thereto in an alkali.

Two or more of the water-soluble polymer compounds may be used incombination. The content of the water-soluble polymer compound ispreferably from 0.1 to 20% by weight, and more preferably from 0.5 to10% by weight, in the developer.

The developer for use in the invention may contain an organic solvent.The organic solvent that can be contained in the developer include, forexample, an aliphatic hydrocarbon (e.g., hexane, heptane, Isopar E,Isopar H, Isopar G (produced by Esso Chemical Co., Ltd.), gasoline orkerosene), an aromatic hydrocarbon (e.g., toluene or xylene), ahalogenated hydrocarbon (methylene dichloride, ethylene dichloride,trichlene or nomochlorobenzene) and a polar solvent.

Examples of the polar solvent include an alcohol (e.g., methanol,ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycolmonomethyl ether, 2-ethyoxyethanol, diethylene glycol monoethyl ether,diethylene glycol monohexyl ether, triethylene glycol monomethyl ether,propylene glycol monoethyl ether, dipropylene glycol monomethyl ether,polyethylene glycol monomethyl ether, polypropylene glycol,tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycolmonobenzyl ether, ethylene glycol monophenyl ether, methyl phenylcarbinol, n-amyl alcohol or methylamyl alcohol), a ketone (e.g.,acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketoneor cyclohexanone), an ester (e.g., ethyl acetate, propyl acetate, butylacetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate,ethylene glycol monobutyl acetate, polyethylene glycol monomethyl etheracetate, diethylene glycol acetate, diethyl phthalate or butyllevulinate) and others (e.g., triethyl phosphate, tricresyl phosphate,N-phenylethanolamine or N-phenyldiethanolamine).

Further, when the organic solvent is insoluble in water, it may beemployed by being solubilized in water using a surfactant or the like.In the case where the developer contains the organic solvent, theconcentration of the organic solvent is desirably less than 40% byweight in view of safety and inflammability.

Into the developer for use in the invention, an antiseptic agent, achelating agent, a defoaming agent, an organic acid, an inorganic acid,an inorganic salt or the like can be incorporated in addition to theabove components.

As the antiseptic agent, for example, phenol or a derivative thereof,formalin, an imidazole derivative, sodium dehydroacetate, a4-isothiazolin-3-one derivative, benzisotiazolin-3-one, a benzotriazolederivative, an amidine guanidine derivative, a quaternary ammonium salt,a pyridine derivative, a quinoline derivative, a guanidine derivative,diazine, a triazole derivative, oxazole, an oxazine derivative and anitro bromo alcohol, e.g., 2-bromo-2-nitropropane-1,3-diol,1,1-dibromo-1-nitro-2-ethanol or 1,1-dibromo-1-nitro-2-propanol arepreferably used.

As the chelating agent, for example, ethylenediaminetetraacetic acid,potassium salt thereof, sodium salt thereof;diethylenetriaminepentaacetic acid, potassium salt thereof, sodium saltthereof; triethylenetetraminehexaacetic acid, potassium salt thereof,sodium salt thereof; hydroxyethylethylenediaminetriacetic acid,potassium salt thereof, sodium salt thereof; nitrilotriacetic acid,sodium salt thereof; organic phosphonic acids, for example,1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodiumsalt thereof; aminotri(methylenephosphonic acid), potassium saltthereof, sodium salt thereof; and phophonoalkanetricarboxylic acids areillustrated. A salt of an organic amine is also effectively used inplace of the sodium salt or potassium salt in the chelating agents.

As the defoaming agent, for example, a conventional silicone-basedself-emulsifying type or emulsifying type defoaming agent, and anonionic surfactant having HLB of 5 or less are used. The siliconedefoaming agent is preferably used. Any of emulsifying dispersing typeand solubilizing type can be used.

As the organic acid, for example, citric acid, acetic acid, oxalic acid,malonic acid, salicylic acid, caprylic acid, tartaric acid, malic acid,lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonicacid, phytic acid and an organic phosphonic acid are illustrated. Theorganic acid can also be used in the form of an alkali metal salt or anammonium salt.

As the inorganic acid and inorganic salt, for example, phosphoric acid,methaphosphoric acid, ammonium primary phosphate, ammonium secondaryphosphate, sodium primary phosphate, sodium secondary phosphate,potassium primary phosphate, potassium secondary phosphate, sodiumtripolyphosphate, potassium pyrophosphate, sodium hexamethaphosphate,magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate,sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite,ammonium sulfite, sodium hydrogen sulfate and nickel sulfate areillustrated.

The developer described above can be used as a developer and adevelopment replenisher for an exposed negative-working lithographicprinting plate precursor, and it is preferably applied to an automaticprocessor described hereinafter. In the case of conducting thedevelopment processing using an automatic processor, the developerbecomes fatigued in accordance with the processing amount, and hence theprocessing ability may be restored using a replenisher or a freshdeveloper. Such a replenishment system can be preferably applied to theplate-making method of the lithographic printing plate precursoraccording to the invention.

The development processing using the aqueous solution having pH of 2 to10 according to the invention is preferably performed by an automaticprocessor equipped with a supplying means for a developer and a rubbingmember. As the automatic processor, there are illustrated an automaticprocessor in which a lithographic printing plate precursor afterimage-recording is subjected to a rubbing treatment while it istransporting described in JP-A-2-220061 and JP-A-60-59351, and anautomatic processor in which a lithographic printing plate precursorafter image-recording placed on a cylinder is subjected to a rubbingtreatment while rotating the cylinder described in U.S. Pat. Nos.5,148,746 and 5,568,768 and British Patent 2,297,719. Among them, theautomatic processor using a rotating brush roll as the rubbing member isparticularly preferred.

The rotating brush roller which can be preferably used in the inventioncan be appropriately selected by taking account, for example, of scratchresistance of the image area and nerve strength of the support of thelithographic printing plate precursor. As for the rotating brush roller,a known rotating brush roller produced by implanting a brush material ina plastic or metal roller can be used. For example, a rotating brushroller described in JP-A-58-159533 and JP-A-3-100554, or a brush rollerdescribed in JP-U-B-62-167253 (the term “JP-UM-B” as used herein meansan “examined Japanese utility model publication”), in which a metal orplastic groove-type member having implanted therein in rows a brushmaterial is closely radially wound around a plastic or metal rolleracting as a core, can be used.

As the brush material, a plastic fiber (for example, a polyester-basedsynthetic fiber, e.g., polyethylene terephthalate or polybutyleneterephthalate; a polyamide-based synthetic fiber, e.g., nylon 6.6 ornylon 6.10; a polyacrylic synthetic fiber, e.g., polyacrylonitrile orpolyalkyl(meth)acrylate; and a polyolefin-based synthetic fiber, e.g.,polypropylene or polystyrene) can be used. For instance, a brushmaterial having a fiber bristle diameter of 20 to 400 μm and a bristlelength of 5 to 30 mm can be preferably used.

The outer diameter of the rotating brush roller is preferably from 30 to200 mm, and the peripheral velocity at the tip of the brush rubbing theplate surface is preferably from 0.1 to 5 m/sec.

Further, it is preferred to use a plurality, that is, two or more of therotating brush rollers.

The rotary direction of the rotating brush roller for use in theinvention may be the same direction or the opposite direction withrespect to the transporting direction of the lithographic printing plateprecursor of the invention, but when two or more rotating brush rollersare used in an automatic processor as shown in FIG. 1, it is preferredthat at least one rotating brush roller rotates in the same directionand at least one rotating brush roller rotates in the opposite directionwith respect to the transporting direction. By such arrangement, thephotosensitive layer in the non-image area can be more steadily removed.Further, a technique of rocking the rotating brush roller in therotation axis direction of the brush roller is also effective.

The developer can be used at an appropriate temperature, and thedeveloper temperature is preferably from 10 to 50° C.

In the invention, the lithographic printing plate after the rubbingtreatment may be subsequently subjected to water washing, a dryingtreatment and an oil-desensitization treatment, if desired. In theoil-desensitization treatment, a known oil-desensitizing solution can beused.

Further, in a plate-making process of the lithographic printing plateprecursor to prepare a lithographic printing plate according to theinvention, the entire surface of the lithographic printing plateprecursor may be heated, if desired, before or during the exposure orbetween the exposure and the development. By the heating, theimage-forming reaction in the photosensitive layer is accelerated andadvantages, for example, improvement in the sensitivity and printingdurability and stabilization of the sensitivity are achieved. For thepurpose of increasing the image strength and printing durability, it isalso effective to perform entire after-heating or entire exposure of theimage after the development. Ordinarily, the heating before thedevelopment is preferably performed under a mild condition of 150° C. orlower. When the temperature is too high, a problem may arise in thatundesirable fog occurs in the non-image area. On the other hand, theheating after the development can be performed using a very strongcondition. Ordinarily, the heat treatment is carried out in atemperature range of 200 to 500° C. When the temperature is too low, asufficient effect of strengthening the image may not be obtained,whereas when it is excessively high, problems of deterioration of thesupport and thermal decomposition of the image area may occur.

The plate-making process is described in more detail below.

In the invention, although the development processing can be carried outjust after the exposure step, the heat treatment step may intervenebetween the exposure step and the development step as described above.The heat treatment is effective for increasing the printing durabilityand improving uniformity of the image hardness degree in the entiresurface of printing plate precursor. The conditions of the heattreatment can be appropriately determined in a range for providing sucheffects. Examples of the heating means include a conventional convectionoven, an IR irradiation apparatus, an IR laser, a microwave apparatus ora Wisconsin oven. For instance, the heat treatment can be conducted bymaintaining the printing plate precursor at a plate surface temperatureranging from 70 to 150° C. for a period of one second to 5 minutes,preferably at 80 to 140° C. for 5 seconds to one minute, more preferablyat 90 to 130° C. for 10 to 30 seconds. In the above-described range, theeffects described above are efficiently achieved and an adverse affect,for example, change in shape of the printing plate precursor due to theheat can be preferably avoided.

According to the invention, the development processing step is conductedafter the exposure step, preferably after the exposure step and the heattreatment step to prepare a lithographic printing plate. It ispreferable that a plate setter used in the exposure step, a heattreatment means used in the heat treatment step and a developmentapparatus used in the development processing step are connected witheach other and the lithographic printing plate precursor is subjected toautomatically continuous processing. Specifically, a plate-making linewherein the plate setter and the development apparatus are connectedwith each other by transport means, for example, a conveyer isillustrated. Also, the heat treatment means may be placed between theplate setter and the development apparatus or the heat treatment meansand the development apparatus may constitute a unit apparatus.

In case where the lithographic printing plate precursor used is apt tobe influenced by surrounding light under a working environment, it ispreferable that the plate-making line is blinded by a filter, a cover orthe like.

After the image formation as described above, the entire surface oflithographic printing plate may be exposed to active ray, for example,ultraviolet light to accelerate hardening of the image area. As a lightsource for the entire surface exposure, for example, a carbon arc lamp,a mercury lamp, a gallium lamp, a metal halide lamp, a xenon lamp, atungsten lamp or various laser beams are exemplified. In order to obtainsufficient printing durability, the amount of the entire surfaceexposure is preferably 10 mJ/cm² or more, more preferably 100 mJ/cm² ormore.

Heating may be performed at the same time with the entire surfaceexposure. By performing the heating, further improvement in the printingdurability is recognized. Examples of the heating means include aconventional convection oven, an IR irradiation apparatus, an IR laser,a microwave apparatus or a Wisconsin oven. The plate surface temperatureat the heating is preferably from 30 to 150° C., more preferably from 35to 130° C., and still more preferably from 40 to 120° C.

In advance of the above-described development processing, thelithographic printing plate precursor is imagewise exposed through atransparent original having a line image, a halftone dot image or thelike, or imagewise exposed, for example, by scanning of laser beam basedon digital data.

The desirable wavelength of the light source is from 350 to 450 nm, andspecifically, an InGaN semiconductor laser is preferably used. Theexposure mechanism may be any of an internal drum system, an externaldrum system and a flat bed system.

Other examples of the exposure light source which can be used in theinvention include an ultra-high pressure mercury lamp, a high pressuremercury lamp, a medium pressure mercury lamp, a low pressure mercurylamp, a chemical lamp, a carbon arc lamp, a xenon lamp, a metal halidelamp, various visible or ultraviolet laser lamps, a fluorescent lamp, atungsten lamp and sunlight.

As for the available laser light source of 350 to 450 nm, the followingscan be used.

A gas laser, for example, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W),Kr ion laser (356 nm, 351 nm, 10 mW to 1 W) and He—Cd laser (441 nm, 325nm, 1 mW to 100 mW); a solid laser, for example, a combination of Nd:YAG(YVO₄) with SHG crystals×twice (355 nm, 5 mW to 1 W) and a combinationof Cr:LiSAF with SHG crystal (430 nm, 10 mW); a semiconductor lasersystem, for example, a KNbO₃ ring resonator (430 nm, 30 mW), acombination of a waveguide-type wavelength conversion element with anAlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), acombination of a waveguide-type wavelength conversion element with anAlGaInP or AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), andAlGaInN (350 nm to 450 nm, 5 mW to 30 mW); a pulse laser, for example,N₂ laser (337 nm, pulse 0.1 to 10 mJ) and XeF (351 nm, pulse 10 to 250mJ) can be used. Among the light sources, the AlGaInN semiconductorlaser (commercially available InGaN semiconductor laser, 400 to 410 nm,5 to 30 mW) is particularly preferable in view of the wavelengthcharacteristics and cost.

As for the exposure apparatus for the lithographic printing plateprecursor of scanning exposure system, the exposure mechanism includesan internal drum system, an external drum system and a flat bed system.As the light source, among the light sources described above, thosecapable of conducting continuous oscillation can be preferably utilized.In practice, the exposure apparatuses described below are particularlypreferable in view of the relationship between the sensitivity ofphotosensitive material and the time for plate-making.

A single beam to triple beam exposure apparatus of internal drum system,using one or more gas or solid laser light sources so as to provide asemiconductor laser having a total output of 20 mW or more

A multi-beam (from 1 to 10 beams) exposure apparatus of flat bed system,using one or more semiconductor, gas or solid lasers so as to provide atotal output of 20 mW or more

A multi-beam (from 1 to 9 beams) exposure apparatus of external drumsystem, using one or more semiconductor, gas or solid lasers so as toprovide a total output of 20 mW or more

A multi-beam (10 or more beams) exposure apparatus of external drumsystem, using one or more semiconductor or solid lasers so as to providea total output of 20 mW or more

In the laser direct drawing-type lithographic printing plate precursor,the following equation (eq 1) is ordinarily established among thesensitivity X (J/cm²) of photosensitive material, the exposure area S(cm²) of photosensitive material, the power q (W) of one laser lightsource, the number n of lasers and the total exposure time t (s):X·S=n·q·t  (eq 1)i) In the case of the internal drum (single beam) system

The following equation (eq 2) is ordinarily established among the laserrevolution number f (radian/s), the sub-scanning length Lx (cm) ofphotosensitive material, the resolution Z (dot/cm) and the totalexposure time t (s):f·Z·t=Lx  (eq 2)ii) In the case of the external drum (multi-beam) system

The following equation (eq 3) is ordinarily established among the drumrevolution number F (radian/s), the sub-scanning length Lx (cm) ofphotosensitive material, the resolution Z (dot/cm), the total exposuretime t (s) and the number (n) of beams:F·Z·n·t=Lx  (eq 3)iii) In the case of the flat bed (multi-beam) system

The following equation (eq 4) is ordinarily established among therevolution number H (radian/s) of polygon mirror, the sub-scanninglength Lx (cm) of photosensitive material, the resolution Z (dot/cm),the total exposure time t (s) and the number (n) of beams:H·Z·n·t=Lx  (eq 4)

When the resolution (2,560 dpi) required for a practical printing plate,the plate size (A1/B1, sub-scanning length: 42 inch), the exposurecondition of about 20 sheets/hour and the photosensitive characteristics(photosensitive wavelength, sensitivity: about 0.1 mJ/cm²) of thelithographic printing plate precursor according to the invention aresubstituted for the above equations, it can be understood that thelithographic printing plate precursor according to the invention ispreferably combined with a multi-beam exposure system using a laserhaving a total output of 20 mW or more, and on taking account ofoperability, cost and the like, most preferably combined with anexternal drum system semiconductor laser multi-beam (10 or more beams)exposure apparatus.

EXAMPLES

The present invention will be described in more detail with reference tothe following examples, but the invention should not be construed asbeing limited thereto.

(Preparation of Support 1)

An aluminum plate (material: JIS A1050) having a thickness of 0.3 mm wasdipped in an aqueous 10% by weight sodium hydroxide solution at 60° C.for 25 seconds to effect etching, washed with running water, neutralizedand cleaned with an aqueous 20% by weight nitric acid solution and thenwashed with water. The aluminum plate was subjected to an electrolyticsurface roughening treatment in an aqueous 1% by weight nitric acidsolution using an alternating current with a sinusoidal waveform at ananode time electricity of 300 coulomb/dm². Subsequently, the aluminumplate was dipped in an aqueous 1% by weight sodium hydroxide solution at40° C. for 5 seconds, dipped in an aqueous 30% by weight sulfuric acidsolution at 60° C. for 40 seconds to effect a desmut treatment, and thensubjected to an anodizing treatment in an aqueous 20% by weight sulfuricacid solution for 2 minutes at a current density of 2 A/dm² to form ananodic oxide film having a thickness of 2.7 g/m². Thereafter, thealuminum plate was treated with an aqueous 1% by weight sodium silicatesolution at 20° C. for 10 seconds.

The center line average roughness (Ra) of the thus-treated aluminumplate was measured using a stylus having a diameter of 2 μm and found tobe 0.25 μm (Ra indication according to JIS B0601).

Further, Undercoat Solution (1) shown below was coated to have a drycoating amount of 10 mg/m² and dried in an oven at 80° C. for 10 secondsto prepare a support having an undercoat layer to be used in theexperiments described below.

<Undercoat Solution (1)> Undercoat Compound (1) shown below 0.017 gMethanol 9.00 g Water 1.00 g Undercoat Compound (1):

[Preparation of Lithographic Printing Plate Precursor (1)]

On the support having an undercoat layer prepared above, CoatingSolution (1) for Photosensitive Layer having the composition shown belowwas coated using a bar and dried in an oven at 70° C. for 60 seconds toform a photosensitive layer having a dry coating amount of 1.1 g/m². Onthe photosensitive layer, Coating Solution (1) for Protective Layerhaving the composition shown below was coated using a bar to have a drycoating amount of 0.75 g/m² and dried at 125° C. for 70 seconds toprepare Lithographic Printing Plate Precursor (1).

<Coating Solution (1) for Photosensitive Layer> Binder Polymer (1) shownbelow (acid value: 0 meq/g; weight 0.54 g average molecular weight:80,000) Polymerizable compound: 0.48 g Dipentaerythritol pentaacrylate(SR399E, produced by Nippon Kayaku Co., Ltd.) Sensitizing Dye (1) shownbelow (absorption maximum 0.06 g wavelength: 364 nm) PolymerizationInitiator (1) shown below 0.18 g Co-sensitizer (1) shown below 0.02 gDispersion of ε-phthalocyanine pigment: 0.40 g (pigment: 15 parts byweight; dispersing agent (Binder Polymer (1)): 10 parts by weight;solvent (cyclohexanone/methoxypropyl acetate/1-methoxy-2-propanol = 15parts by weight/20 parts by weight/40 parts by weight)) Thermalpolymerization inhibitor: 0.01 g N-nitrosophenylhydroxylamine aluminumsalt Fluorine-Based Surfactant (1) shown below 0.001 gPolyoxyethylene-polyoxypropylene condensate 0.04 g (Pluronic L44,produced by ADEKA Corp.) Tetraethylamine hydrochloride 0.01 g1-Methoxy-2-propanol 3.5 g Methyl ethyl ketone 8.0 g Binder Polymer (1):

Sensitizing Dye (1):

Polymerization Initiator (1):

Co-sensitizer (1):

Fluorine-Based Surfactant (1):

<Coating Solution (1) for Protective Layer> Polyvinyl alcohol(saponification degree: 98% by mole; 40 g polymerization degree: 500)Polyvinyl pyrrolidone (molecular weight: 50,000) 5 g Vinylpyrrolidone/vinyl acetate (1/1) copolymer (molecular 0.5 g weight:70,000) Surfactant (polyoxyethylene lauryl ether: Emalex 710, 0.5 gproduced by Nihon-Emulsion Co., Ltd.) Water 950 g[Preparation of Lithographic Printing Plate Precursor (2)]

Lithographic Printing Plate Precursor (2) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Binder Polymer (1) in Coating Solution (1) forPhotosensitive Layer to Binder Polymer (5) (acid value: 1.9 meq/g;weight average molecular weight: 80,000) shown below.Binder Polymer (5):

[Preparation of Lithographic Printing Plate Precursor (3)]

Lithographic Printing Plate Precursor (3) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Coating Solution (1) for Photosensitive Layer toCoating Solution (2) for Photosensitive Layer having the compositionshown below.

<Coating Solution (2) for Photosensitive Layer> Polymerization Initiator(1) shown above 0.2 g Sensitizing Dye (1) shown above 0.1 g BinderPolymer (1) shown above (average molecular weight: 3.0 g 80,000)Polymerizable compound: Isocyanuric acid EO-modified diacrylate (Aronics6.2 g M-215, produced by Toa Gosei Co., Ltd.) Leuco Crystal Violet 0.2 gFluorine-based Surfactant (1) shown above 0.1 g Dispersion ofMicrocapsule (1) shown below 25.0 g Methyl ethyl ketone 35.0 g1-Methoxy-2-propanol 35.0 g(Preparation of Dispersion of Microcapsule (1))

As an oil phase component, 10 g of adduct of trimethylolpropane andxylene diisocyanate (Takenate D-110N, produced by Mitsui TakedaChemicals, Inc.), 4.15 g of dipentaerythritol pentaacrylate (SR399E,produced by Nippon Kayaku Co., Ltd.) and 0.1 g of Pionin A-41C (producedby Takemoto Oil & Fat Co., Ltd.) were dissolved in 17 g of ethylacetate. As an aqueous phase component, 40 g of an aqueous 4% by weightPVA-205 solution was prepared. The oil phase component and the aqueousphase component were mixed and emulsified using a homogenizer at 12,000rpm for 10 minutes. The resulting emulsion was added to 25 g ofdistilled water and the mixture was stirred at room temperature for 30minutes and then stirred at 40° C. for 3 hours. The thus-obtainedmicrocapsule solution was diluted with distilled water to have a solidcontent concentration of 20% by weight to prepare Dispersion ofMicrocapsule (1). The average particle diameter of the microcapsule was0.25 μm.

[Preparation of Lithographic Printing Plate Precursor (4)]

Lithographic Printing Plate Precursor (4) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Binder Polymer (1) in Coating Solution (1) forPhotosensitive Layer to Binder Polymer (2) (acid value; 0 meq/g; weightaverage molecular weight: 70,000) shown below.

[Preparation of Lithographic Printing Plate Precursor (5)]

Lithographic Printing Plate Precursor (5) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Binder Polymer (1) in Coating Solution (1) forPhotosensitive Layer to Binder Polymer (3) (acid value; 0 meq/g; weightaverage molecular weight: 100,000) shown below.

[Preparation of Lithographic Printing Plate Precursor (6)]

Lithographic Printing Plate Precursor (6) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Binder Polymer (1) in Coating Solution (1) forPhotosensitive Layer to Binder Polymer (4) (acid value; 0 meq/g; weightaverage molecular weight: 90,000) shown below.Binder Polymer (2):

Binder Polymer (3):

Binder Polymer (4):

[Preparation of Lithographic Printing Plate Precursor (7)]

Lithographic Printing Plate Precursor (7) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Co-sensitizer (1) in Coating Solution (1) forPhotosensitive Layer to Co-sensitizer (2) shown below.Co-Sensitizer (2):

[Preparation of Lithographic Printing Plate Precursor (8)]

Lithographic Printing Plate Precursor (8) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Co-sensitizer (1) in Coating Solution (1) forPhotosensitive Layer to Co-sensitizer (3) shown below.Co-Sensitizer (3):

[Preparation of Lithographic Printing Plate Precursor (9)]

Lithographic Printing Plate Precursor (9) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Coating Solution (1) for Protective Layer toCoating Solution (2) for Protective Layer having the composition shownbelow and coating using a bar to have a dry coating amount of 0.2 g/M².

<Coating Solution (2) for Protective Layer> Dispersion of Mica (1) shownbelow 13.0 g Polyvinyl alcohol (saponification degree: 98% by mole; 1.3g polymerization degree: 500) Sodium 2-ethylhexylsulfosuccinate 0.2 gVinyl pyrrolidone/vinyl acetate (1/1) copolymer (molecular 0.05 gweight: 70,000) Surfactant (Emalex 710, produced by Nihon-Emulsion Co.,0.05 g Ltd.) Water 133 g(Preparation of Dispersion of Mica (1))

In 368 g of water was added 32 g of synthetic mica (SOMASIF ME-100,produced by CO-OP Chemical Co., Ltd.; aspect ratio: 1,000 or more) anddispersed using a homogenizer until the average particle diameter(measured by a laser scattering method) became 0.5 μm to obtainDispersion of Mica (1).

[Preparation of Lithographic Printing Plate Precursor (10)]

Lithographic Printing Plate Precursor (10) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Support 1 to Support 2 shown below.

(Preparation of Support 2)

An aluminum plate (material: JIS A1050) having a thickness of 0.3 mm wassubjected to a degrease treatment with an aqueous 10% by weight sodiumaluminate solution at 50° C. for 30 seconds in order to remove rollingoil on the surface thereof. Thereafter, the aluminum plate surface wasgrained using three nylon brushes implanted with bundled bristles havinga diameter of 0.3 mm and an aqueous suspension (specific gravity: 1.1g/cm³) of pumice having a median diameter of 25 μm, and then thoroughlywashed with water. The plate was etched by dipping it in an aqueous 25%by weight sodium hydroxide solution at 45° C. for 9 seconds and afterwashing with water, dipped in an aqueous 20% by weight nitric acidsolution at 60° C. for 20 seconds, followed by washing with water. Theetching amount of the grained surface was about 3 g/m².

Subsequently, the aluminum plate was subjected to a continuouselectrochemical surface roughening treatment using alternate currentvoltage of 60 Hz. The electrolytic solution used was an aqueous 1% byweight nitric acid solution (containing 0.5% by weight of aluminum ion)at a liquid temperature of 50° C. The electrochemical surface rougheningtreatment was performed using a rectangular wave alternate currenthaving a trapezoidal waveform such that the time TP necessary for thecurrent value to reach the peak from zero was 0.8 msec and the dutyratio was 1:1, and disposing a carbon electrode as the counterelectrode. The auxiliary anode used was ferrite. The current density was30 A/dm² in terms of the peak value of current, and 5% of the currentflowing from the power source was divided to the auxiliary anode. Thequantity of electricity at the nitric acid electrolysis was 175 C/dm²when the aluminum plate was serving as the anode. Then, the aluminumplate was washed with water by spraying.

Then, the aluminum plate was subjected to an electrochemical surfaceroughening treatment in the same manner as in the nitric acidelectrolysis above using, as the electrolytic solution, an aqueous 0.5%by weight hydrochloric acid solution (containing 0.5% by weight ofaluminum ion) at a liquid temperature of 50° C. under the conditionsthat the quantity of electricity was 50 C/dm² when the aluminum platewas serving as the anode, and then washed with water by spraying. Theplate was then treated in an aqueous 15% by weight sulfuric acidsolution (containing 0.5% by weight of aluminum ion) as the electrolyticsolution at a current density of 15 A/dm² to provide a direct currentanodic oxide film of 2.5 g/m², thereafter washed with water and dried.Then, the aluminum plate was treated with an aqueous 1% by weight sodiumsilicate solution at 20° C. for 10 seconds.

The center line average roughness Ra of the thus-treated aluminum platewas measured using a stylus having a diameter of 2 μm and found to be0.51 μm (Ra indication according to JIS B0601).

On the aluminum plate thus-treated was coated Undercoat Solution (2)having the composition shown below using a bar to have a dry coatingamount of 10 mg/m², followed by drying in an oven at 80° C. for 20seconds, thereby preparing Support 2.

<Undercoat Solution (2)> Sol solution shown below 100 g Methanol 900 gSol Solution Phosmer PE (produced by Uni-Chemical Co., Ltd) 5 g Methanol45 g Water 10 g Phosphoric acid (85% by weight) 5 g Tetraethoxysilane 20g 3-Methacryloxypropyltrimethoxysilane 15 g[Preparation of Lithographic Printing Plate Precursor (11)]

Lithographic Printing Plate Precursor (11) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Sensitizing Dye (1) in Coating Solution (1) forPhotosensitive Layer to Sensitizing Dye (2) shown below.Sensitizing Dye (2):

[Preparation of Lithographic Printing Plate Precursor (12)]

Lithographic Printing Plate Precursor (12) was prepared in the samemanner as in the preparation of Lithographic Printing Plate Precursor(1) except for changing Sensitizing Dye (1) in Coating Solution (1) forPhotosensitive Layer to Sensitizing Dye (3) shown below. The absorptionmaximum wavelength of Sensitizing Dye (3) is 387 nm.Sensitizing Dye (3):

Examples 1 to 9 and 13 and Comparative Examples 1 to 2

(1) Exposure, Development and Printing

Each of Lithographic Printing Plate Precursors (1) to (12) was subjectedto imagewise exposure using a semiconductor laser of 405 nm having anoutput of 100 mW while changing energy density.

Then, development processing was performed in an automatic developmentprocessor having a structure shown in FIG. 1 using Developer (1) havingthe composition shown below. The pH of the developer was 5. Theautomatic development processor was an automatic processor having tworotating brush rollers. As for the rotating brush rollers used, thefirst brush roller was a brush roller having an outer diameter of 50 mmand being implanted with fiber of polybutylene terephthalate (bristlediameter: 200 μm, bristle length: 17 mm), and the brush roller wasrotated at 200 rpm in the same direction as the transporting direction(peripheral velocity at the tip of brush: 0.52 m/sec). The second brushroller was a brush roller having an outer diameter of 50 mm and beingimplanted with fiber of polybutylene terephthalate (bristle diameter:200 μm, bristle length: 17 mm), and the brush roller was rotated at 200rpm in the opposite direction to the transporting direction (peripheralvelocity at the tip of brush: 0.52 m/sec). The transportation of thelithographic printing plate precursor was performed at a transportingspeed of 100 cm/min.

The developer was supplied on the surface of the lithographic printingplate precursor by showering from a spray pipe using a circulation pump.The tank volume for the developer was 10 liters.

Developer (1) Water 100 g Benzyl alcohol 1 g Polyoxyethylene naphthylether (average number of 1 g oxyethylene: n = 13) (Newcol B13, producedby Nippon Nyukazai Co., Ltd.) Sodium salt of dioctylsulfosuccinic acidester 0.5 g Gum arabic 1 g Ethylene glycol 0.5 g Ammonium primaryphosphate 0.05 g Citric acid 0.05 g Tetrasodium salt ofethylenediaminetetraacetate 0.05 g

The lithographic printing plate after development was mounted on aprinting machine, SOR-M, produced by Heidelberg, and printing wasperformed at a printing speed of 6,000 sheets per hour using dampeningwater (EU-3 (etching solution, produced by Fuji Photo Film Co.,Ltd.))/water/isopropyl alcohol=1/89/10 (by volume ratio)) and TRANS-G(N)black ink (produced by Dai-Nippon Ink & Chemicals, Inc.).

(2) Evaluation

Using the lithographic printing plate precursors prepared above, thesensitivity, developing property and safelight aptitude were evaluatedin the following manner.

<Sensitivity>

After performing printing of 100 sheets as described above andconfirming that a printed material free from ink stain in the non-imagearea was obtained, 500 sheets were continuously printed. Thus, 600sheets in total were printed. The exposure amount for causing nounevenness in the ink density of the image area on the 600th printedmaterial was determined and defined as the sensitivity.

<Developing Property>

The lithographic printing plate precursor prepared was subjected to theimage exposure and development processing in the same manner asdescribed above. After the development processing, the non-image area ofthe lithographic printing plate was visually observed and the presenceor absence of the residue of the photosensitive layer was evaluated.

<Safelight Aptitude>

The lithographic printing plate precursor prepared was exposed under ayellow lamp (a fluorescent lamp cutting wavelength of 500 nm or shorter;illuminance: 250 lux) for 10 minutes, 20 minutes or 30 minutes beforeimage exposure and subsequently subjected to the image exposure anddevelopment processing in the same manner as described above. After thedevelopment processing, the non-image area of the lithographic printingplate was visually observed and the presence or absence of the formationof fog (residue of the photosensitive layer) was evaluated.

The results obtained are shown in Table 1. TABLE 1 Lithographic PrintingPlate Developing Sensitivity Safelight Aptitude Precursor Property(mJ/cm²) 10 Minutes 20 Minutes 30 Minutes Example 1 1 ◯ 0.20 ◯ ◯ ◯Comparative 2 X Unable to Unable to Unable to Unable to evaluate Example1 evaluate evaluate evaluate Example 2 3 ◯ 0.25 ◯ ◯ ◯ Example 3 4 ◯ 0.20◯ ◯ ◯ Example 4 5 ◯ 0.20 ◯ ◯ ◯ Example 5 6 ◯ 0.15 ◯ ◯ ◯ Example 6 7 ◯0.15 ◯ ◯ ◯ Example 7 8 ◯ 0.10 ◯ ◯ ◯ Example 8 9 ◯ 0.20 ◯ ◯ ◯ Example 910 ◯ 0.25 ◯ ◯ ◯ Comparative 11 ◯ 0.5 ◯ ◯ ◯ Example 2 Example 10 1 ◯ 0.20◯ ◯ X Example 11 1 ◯ 0.20 ◯ ◯ ◯ Example 12 1 ◯ 0.20 ◯ ◯ ◯ Example 13 12◯ 0.20 ◯ ◯ ◯◯: No occurrence of fogX: Occurrence of fog

Example 10

The image exposure, development processing and printing were conductedin the same manner as in Example 1 except that the developmentprocessing was carried out by the automatic development processor inwhich the two rotating brush rollers were detached. As a result, thesafelight aptitude was somewhat deteriorated as shown in Table 1.

Example 11

The image exposure, development processing and printing were conductedin the same manner as in Example 1 except for changing thepolyoxyethylene naphthyl ether used in Developer (1) to an anionicsurfactant having the structure shown below (polyoxyethylene naphthylether sulfuric ester salt, Newcol B4SN, produced by Nippon Nyukazai Co.,Ltd.) and further adding 0.1 g of a defoaming agent, FS Antifoam DR110N(produced by Dow Coming Corp., silicone-based emulsion). As a result,the evaluation results similar to those in Example 1 were obtained. ThepH of the developer was 5.Anionic Surfactant:

Example 12

The image exposure, development processing and printing were conductedin the same manner as in Example 1 except for changing Developer (1) toDeveloper (2) having the composition shown below. As a result, theevaluation results similar to those in Example 1 were obtained. The pHof the developer was 4.5.

Developer (2) Water 100 g Sodium alkylnaphthalenesulfonate (Pelex NB-L,produced 5 g by Kao Corp.) Gum arabic 1 g Ammonium primary phosphate0.05 g Citric acid 0.05 g Tetrasodium salt ofethylenediaminetetraacetate 0.05 g

Example 14

The image exposure, development processing and printing were conductedin the same manner as in Example 12 except that within 30 seconds afterthe image exposure, the exposed lithographic printing plate precursorwas put in an oven and heated the whole surface of the lithographicprinting plate precursor by blowing hot air to maintain at 110° C. for15 seconds and after that the development processing was performedwithin 30 seconds in the same manner as in Example 12.

The sensitivity was changed to 0.09 mJ/cm² by conducting the heattreatment and the developing property and safelight aptitude were goodwithout the residue of the photosensitive layer in the non-image area.

Example 15

Lithographic Printing Plate Precursor (1) was subjected to imageexposure by a violet semiconductor laser plate setter V×9600 (havingInGaN semiconductor laser: emission: 405 nm±10 nm/output: 30 mW,produced by FUJIFILM Electronic Imaging, Ltd.). As for the image,halftone dots of 35% were drawn using an FM screen (TAFFETA 20, producedby Fuji Photo Film Co., Ltd.) in a plate surface exposure amount of 0.09mJ/cm² and at resolution of 2,438 dpi. The exposed lithographic printingplate precursor was subjected to development processing within 30seconds after the image exposure using an automatic processor(LP1250PLX, produced by Fuji Photo Film Co., Ltd.). The automaticprocessor was composed of a heating unit, a water-washing unit, adeveloping unit, a rinsing unit and a finishing unit in this order. Theheating condition in the heating unit was 100° C. for 10 seconds. In allbathes of the water-washing unit, developing unit, rinsing unit andfinishing unit, Developer (2) described above was charged. Thetemperature of the developer was 28° C. and the transportation of thelithographic printing plate precursor was performed at a transportingspeed of 110 cm/min.

After the development processing, the non-image area and image area ofthe resulting lithographic printing plate were visually observed. As aresult, it was found that the residue of the photosensitive layer wasnot present in the non-image area and the uniform halftone dot imagefree from unevenness was formed. Further, the printing was conductedusing the lithographic printing plate under the same conditions asdescribed above. As a result, good printed materials of uniform halftonedot image free from unevenness and without stain in the non-image areawere obtained.

Example 16

The image exposure, development processing and printing were conductedin the same manner as in Example 1 except for changing Developer (1) toDeveloper (3) shown below. As a result, the evaluation results similarto those in Example 1 were obtained. The pH of Developer (3) was 4.0.

Developer (3) Water 100 g Polyoxyethylene laurylamino ether (PaioninD3110, 10 g produced by Takemoto Oil and Fat Co., Ltd.)Polystyrenesulfonic acid 1 g Ammonium primary phosphate 0.05 g Citricacid 0.05 g Tetrasodium salt of ethylenediaminetetraacetate 0.05 g

Example 17

The image exposure, development processing and printing were conductedin the same manner as in Example 16 except for changing thepolyoxyethylene laurylamino ether (Paionin D3110, produced by TakemotoOil and Fat Co., Ltd.) in Developer (3) to N-lauryldimethyl betaine(Paionin C157K, produced by Takemoto Oil and Fat Co., Ltd.). As aresult, the evaluation results similar to those in Example 16 wereobtained. The pH of the developer was 4.0.

Example 18

Lithographic Printing Plate Precursor (1) was subjected to the imageexposure and development processing in the same manner as in Example 15except that Developer (3) was charged in the bathes of the developingunit and finishing unit and water was charged in the baths of thewater-washing unit and rinsing unit in place of Developer (2).

After the development processing, the non-image area and image area ofthe resulting lithographic printing plate were visually observed. As aresult, it was found that the residue of the photosensitive layer wasnot present in the non-image area and the uniform halftone dot imagefree from unevenness was formed. Further, the printing was conductedusing the lithographic printing plate under the same conditions asdescribed above. As a result, good printed materials of uniform halftonedot image free from unevenness and without stain in the non-image areawere obtained.

Examples 19 to 23

An aqueous 8% by weight solution of each surfactant shown in Table 2below was prepared. Lithographic Printing Plate Precursor (1) wasimmersed in each of the solutions while changing the immersion time at5-second intervals. After the immersion, the surface of the lithographicprinting precursor was rubbed with a sponge, followed by washing withwater. The immersion time necessary for removing the photosensitivelayer was determined and evaluated as the developing time. As theimmersion time is shorter, the developing property is better. TABLE 2Devel- oping Surfactant Time (sec) Example Polyoxyethylene naphthylether (Newcol B13, 20 19 produced by Nippon Nyukazai Co., Ltd.) ExamplePolyoxyethylene naphthyl ether sulfuric ester salt 15 20 (Newcol B4SN,produced by Nippon Nyukazai Co., Ltd.) Example Sodiumalkylnaphthalenesulfonate (Pelex NB-L, 15 21 produced by Kao Corp.)Example Polyoxyethylene laurylamino ether (Paionin 10 22 D3110, producedby Takemoto Oil and Fat Co., Ltd.) Example N-Lauryldimethyl betaine(Paionin C157K, 15 23 produced by Takemoto Oil and Fat Co., Ltd.)

From the results shown above, it can be seen that favorable developmentcan be conducted by using the developer containing the specificpreferable surfactant.

This application is based on Japanese Patent application JP 2005-349608,filed Dec. 2, 2005 and Japanese Patent application JP 2006-123824, filedApr. 27, 2006, the entire contents of which are hereby incorporated byreference, the same as if set forth at length.

1. A method for preparing a lithographic printing plate comprising:exposing a lithographic printing plate precursor comprising ahydrophilic support, a photosensitive layer containing (A) a sensitizingdye having an absorption maximum in a wavelength range of from 350 to450 nm represented by the following formula (I) or (II), (B) apolymerization initiator, (C) a polymerizable compound and (D) ahydrophobic binder polymer having an acid value of 0.3 meq/g or less anda protective layer provided in this order with a laser beam of from 350to 450 nm; and rubbing a surface of the exposed lithographic printingplate precursor with a rubbing member in a presence of a developerhaving pH of from 2 to 10 in an automatic processor equipped with therubbing member to remove the protective layer and an unexposed area ofthe photosensitive layer:

wherein R¹ to R¹⁴ each independently represents a hydrogen atom, analkyl group, an alkoxy group, a cyano group or a halogen atom, providedthat at least one of R¹ to R¹⁰ represents an alkoxy group having 2 ormore carbon atoms; and R¹⁵ to R³² each independently represents ahydrogen atom, an alkyl group, an alkoxy group, a cyano group or ahalogen atom, provided that at least one of R¹⁵ to R²⁴ represents analkoxy group having 2 or more carbon atoms.
 2. The method as claimed inclaim 1, wherein the polymerization initiator is a hexaarylbiimidazolecompound.
 3. The method as claimed in claim 2, wherein thephotosensitive layer further contains (E) a chain transfer agent.
 4. Themethod as claimed in claim 3, wherein (E) the chain transfer agent is athiol compound represented by the following formula (T):

wherein R represents an alkyl group which may have a substituent or anaryl group which may have a substituent; and A represents an atomicgroup necessary for forming a 5-membered or 6-membered hetero ringcontaining a carbon atom together with the N═C—N linkage, and A may havea substituent.
 5. The method as claimed in claim 1, wherein thehydrophobic binder polymer is at least one member selected from thegroup consisting of a (meth)acrylic copolymer having a crosslinkablegroup in a side chain or a polyurethane resin having a crosslinkablegroup in a side chain.
 6. The method as claimed in claim 1, wherein apart or all of components of the photosensitive layer is encapsulated ina microcapsule.
 7. The method as claimed in claim 1, wherein the rubbingmember comprises at least two rotating brush rollers.
 8. The method asclaimed in claim 1, wherein the pH of the developer is from 3 to
 8. 9.The method as claimed in claim 1, wherein the exposed lithographicprinting plate precursor is subjected to a heat treatment between theexposing and the rubbing.
 10. The method as claimed in claim 1, whereinthe developer contains a surfactant represented by the following formula(III) or (IV):

wherein R₁ to R₁₀ each independently represents a hydrogen atom or analkyl group; I represents an integer of from 1 to 3; X₁ and X₂ eachindependently represents a sulfonate, a sulfuric monoester salt, acarboxylate or a phosphate; and provided that a total number of carbonatoms included in R₁ to R₅ or R₆ to R₁₀ is 3 or more.
 11. The method asclaimed in claim 1, wherein the developer contains a surfactantrepresented by the following formula (V) or (VI):

wherein R₁ to R₁₀ each independently represents a hydrogen atom or analkyl group; 1 represents an integer of from 1 to 3; X₁ and X₂ eachindependently represents a sulfonate, a sulfuric monoester salt, acarboxylate or a phosphate; Y₁ and Y₂ each independently represents—C_(n)H_(2n)—, —C_(n−m)H_(2(n−m))OC_(m)H_(2m)—, —O—(CH₂CH₂O)_(n)—,—O—(CH₂CH₂CH₂O)_(n)— or —CO—NH— wherein n≧1 and n≧m≧0; and provided thata total number of carbon atoms included in R₁ to R₅ and Y₁ or R₆ to R₁₀and Y₂ is 3 or more.
 12. The method as claimed in claim 1, wherein thedeveloper contains a surfactant represented by one of the followingformulae (VII) to (IX):

wherein R_(a) represents a hydrogen atom or an alkyl group; A and B eachindependently represents a group containing an ethylene oxide group, acarboxylic acid group or a carboxylate; R_(b) and R_(c) eachindependently represents a hydrogen atom or an alkyl group; C representsan alkyl group or a group containing an ethylene oxide group; Drepresents a group containing a carboxylic acid anion; R_(d), R_(e),R_(f) and R_(g) each independently represents a hydrogen atom or analkyl group; and Z⁻ represents a counter anion.
 13. A lithographicprinting plate precursor comprising: a hydrophilic support; aphotosensitive layer containing (A) a sensitizing dye having anabsorption maximum in a wavelength range of from 350 to 450 nmrepresented by the following formula (I) or (II), (B) a polymerizationinitiator, (C) a polymerizable compound and (D) a hydrophobic binderpolymer having an acid value of 0.3 meq/g or less; and a protectivelayer provided in this order, wherein the protective layer and anunexposed area of the photosensitive layer are capable of being removedby exposing the lithographic printing plate precursor with a laser beamof from 350 to 450 nm and rubbing a surface of the exposed lithographicprinting plate precursor with a rubbing member in a presence of adeveloper having pH of from 2 to 10 in an automatic processor equippedwith the rubbing member:

wherein R¹ to R¹⁴ each independently represents a hydrogen atom, analkyl group, an alkoxy group, a cyano group or a halogen atom, providedthat at least one of R¹ to R¹⁰ represents an alkoxy group having 2 ormore carbon atoms; and R¹⁵ to R³² each independently represents ahydrogen atom, an alkyl group, an alkoxy group, a cyano group or ahalogen atom, provided that at least one of R¹⁵ to R²⁴ represents analkoxy group having 2 or more carbon atoms.
 14. The lithographicprinting plate precursor as claimed in claim 13, wherein thepolymerization initiator is a hexaarylbiimidazole compound.
 15. Thelithographic printing plate precursor as claimed in claim 14, whereinthe photosensitive layer further contains (E) a chain transfer agent.16. The lithographic printing plate precursor as claimed in claim 15,wherein the chain transfer agent is a thiol compound represented by thefollowing formula (T):

wherein R represents an alkyl group which may have a substituent or anaryl group which may have a substituent; and A represents an atomicgroup necessary for forming a 5-membered or 6-membered hetero ringcontaining a carbon atom together with the N═C—N linkage, and A may havea substituent.
 17. The lithographic printing plate precursor as claimedin claim 13, wherein the exposed lithographic printing plate precursoris subjected to a heat treatment between the exposing and the rubbing.